Herbicidal aryl triazolinones

ABSTRACT

Herbicidal aryl triazolinones include the compounds of the formula ##STR1## where X is preferably halogen such as fluorine, Y is preferably halogen such as chlorine, R 1  is preferably methyl, R 2  is preferably CHF 2 , R 3  is preferably CH(CH 3 ). Z is oxygen or sulfur. R 4  may be alkyl, substituted alkyl, alkenyl, alkynyl, monovalent cyclic having a ring of 5 or 6 atoms or ZR 4  may be a residue of an amine, a sulfonamide, or an oxime.

This application is a continuation-in-part of Ser. No. 666,933, filedOct. 31, 1984, now abandoned.

The invention described in this application pertains to weed control inagriculture, horticulture, and other fields where there is a desire tocontrol unwanted plant growth. More specifically, the presentapplication describes certain herbicidal aryl triazolinones,compositions of them, methods of preparing them, and methods forpreventing or destroying undesired plant growth by preemergence orpostemergence application of the herbicidal compositions to the locuswhere control is desired. The present compounds may be used toeffectively control a variety of bothh grassy and broadleaf plantspecies. The present invention is particularly useful in agriculture; anumber of the compounds described herein show a selectivity favorable tocertain crops at application levels which inhibit the growth of ordestroy a variety of weeds.

One aspect of this invention relates to herbicidal compounds of thegeneral formula ##STR2## wherein R² is CHF₂ or CH₂ F;

X is bromine, chlorine, or fluorine or haloalkyl (e.g. CF₃);

R¹ may be halogen (e.g. chlorine), alkyl (e.g. of 1 to 5 carbon atoms),haloalkyl (e.g. of 1 to 5 carbon atoms such as difluoromethyl),alkoxyalkyl (e.g. of 2 to 6 carbon atoms such as methoxymethyl),cyanoalkyl (e.g. of 2 to 6 carbon atoms such as cyanomethyl), arylalkylsuch as benzyl, alkylthio (e.g. of 1 to 3 carbon atoms such asmethylthio) or the corresponding alkylsulfinyl or alkylsulfonyl, oralkylthioalkyl (e.g., of 1 to 3 carbon atoms independently with respectto each alkyl, such as methylthiomethyl) or the correspondingalkylsulfinylalkyl or alkylsulfonylalkyl.

Y is bromine, chlorine, fluorine, methyl, haloalkyl (e.g. FCH₂), aradical of the formula R⁸ OCH₂ --, R⁸ SCH₂ --, R⁸ SOCH₂ -- or R⁸ SO₂ CH₂-- where R⁸ is C₁ -C₃ alkyl, C₂ -C₅ alkenyl, or C₃ -C₅ alkynyl (e.g.,CH₃ OCH₂ --, CH₃ SCH₂ --, CH₂ ═CHCH₂ OCH₂ --, CH₂ ═CHCH₂ SCH₂ --,CH.tbd.CCH₂ OCH₂ --, or CH.tbd.C--CH₂ SCH₂ --); R₈ may also be phenyl(or phenyl substituted with e.g., halogen, alkyl, haloalkyl; see, e.g.compound 50, below).

R³ is an alkylene radical (e.g. a lower alkylene such as --CH₂ -- or--CH(CH₃)--) or a haloalkylene radical (e.g. --CHF--) and R⁴ is an alkylradical (e.g. CH₃, C₂ H₅, C₃ H₇, C₄ H₉).

It is preferred that R¹ be methyl and R² be CHF₂ and particularly that Xbe chlorine or (more preferably) fluorine and Y be chlorine.

Some of the compounds described above differ from otherwise similarcompounds disclosed in U.S. Pat. No. 4,318,731 in that R² of that patentis hydrogen, an alkyl group, or an alkenyl group. It has been found nowthat the replacement of an alkyl group by a CHF₂ or CH₂ F group yieldscompounds of much greater herbicidal activity. This is shown, forinstance, in Table I below which gives the results of tests of thefollowing two compounds, each applied at the rate of 0.125 kg. perhectare:

A. A compound in which R² is CHF₂ (compound No. 5 described below).

B. An otherwise identical compound in which R² is C₂ H₅ (compound 62 ofthe aforesaid U.S. patent).

Representative compounds according to this aspect of the invention aregiven in Table 2 below.

The herbicidal esters of the aspect of the invention described above maybe hydrolyzed to produce the corresponding acids, i.e., to compounds ofthe foregoing formula in which the substituent para to "X" is --OR³ COOH(i.e. carboxyalkoxy). I have found that these acids are also effectiveherbicides, somewhat less potent than the corresponding esters. Theacids are also useful as intermediates for the preparation (as byesterification or amide formation) of other herbicidal compounds. Theacids may be converted to their salts, such as their sodium, potassium,ammonium, calcium, magnesium, or mono, di or trialkylammonium salts,which may be used as herbicides.

Representative acids and salts are shown in Table 3 below.

In another aspect of this invention it has now been found that compoundsof the following formula are effective herbicidal compounds: ##STR3##wherein R⁴ is a substituted alkyl group, an alkenyl group (e.g. allyl ormethallyl) or an alkynyl group (e.g., propargyl) or a monovalent cyclicgroup having a ring of 5 or 6 atoms (e.g. an aromatic or heterocyclic oralicyclic ring) whose valence is on a carbon atom of said ring, and Z isO or S. Corresponding compounds in which Z is sulfur and R⁴ isunsubstituted alkyl (e.g. of 1-4 carbon atoms) have also been found tobe effective herbicides. With respect to R⁴, examples of suitablesubstituents on the alkyl group are:

nitro;

halo (Cl, F, Br);

furyl or tetrahydrofuryl;

acetyl (CH₃ CO);

--CO--N(R^(II))(R^(III)) where --N(R^(II))(R^(III)) is the residue(minus hydrogen) of ammonia or of a primary or secondary amine (e.g.methylamine, dimethylamine or other lower alkylamine);

cyano;

--COOR^(IV) where R^(IV) is the residue of an alcohol (such as theresidue of a lower alkanol, e.g. a methyl or ethyl radical);

phenyl or substituted phenyl;

alkylamino, dialkylamino or a trialkylammonium salt (such as that shownin compound no. B20 below);

alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl (in which radicals thealkyl is preferably methyl or other lower alkyl) or phenoxy, phenylthio,phenylsulfinyl, or phenylsulfonyl (in which radicals the phenyl moietymay be substituted or unsubstituted).

When R⁴ is alkenyl or alkynyl it may be substituted with one of theforegoing substituents.

For the substituted phenyls mentioned above the substituents may be, forinstance, alkyl, haloalkyl, alkoxy, alkylthio, alkylsulfinyl,alkylsulfonyl, halogen, cyano, nitro, hydroxy, amino or alkyl ordialkylamino or carboxyl.

It is preferred that X, Y, R¹ and R² be as defined above for Formula I,and particularly that X be chlorine or (more preferably) fluorine, Y bechlorine, R¹ be methyl and R² be CHF₂. However, within the broader scopeof this aspect of the invention R² substituents may be alkyl (e.g. of 1to 5 carbon atoms), haloalkyl (e.g. of 1 to 5 carbon atoms, such asCHF₂), alkenyl of 2 to 5 carbon atoms (e.g. allyl), alkynyl of 3 to 5carbon atoms (e.g. propargyl), cyanoalkyl (e.g. CH₂ CN or CH₂ CH₂ CN),thiocyanoalkyl (e.g. CH₂ SCN) or a group of the formula -alkylene-Y¹ -R⁵in which said alkylene group (e.g. --CH₂ --) has 1 to 5 carbon atoms, Y¹being oxygen or S(O)_(r) in which r is 0 to 2, and R⁵ being alkyl (e.g.of 1 to 5 carbon atoms such as methyl), alkenyl of 2 to 5 carbon atoms(e.g. allyl) or alkynyl of 3 to 5 carbon atoms (such as propargyl).

Representative compounds according to this aspect of the invention areshown in Table 4 below.

In still another aspect of this invention it has now been found thatcompounds of the following formula are effective herbicidal compounds:##STR4## in which R³ is an alkylene radical (e.g. --CH₂ -- or--CH(CH₃)--) or a haloalkylene radical (e.g. --CHF--), and ##STR5## is--NH₂ or the residue of a primary or secondary amine or of asulfonamide. For instance, R⁶ and R⁷ may be, each, independently, H,alkyl, alkenyl, alkynyl, cycloalkyl, aryl, alkoxy, alkylsulfonyl,haloalkylsulfonyl, cycloalkylsulfonyl, arylsulfonyl (includingheteroarylsulfonyl such as thienylsulfonyl), aralkylsulfonyl,aminosulfonyl, dialkylaminosulfonyl, alkylaminosulfonyl,alkenylsulfonyl, phenylalkenylsulfonyl. R⁶ may be bicyclic or polycyclicsuch as benzofuranyl, dihydrobenzofuranyl benzofuransulfonyl,dihydrobenzofuransulfonyl, naphthalenesulfonyl, benzodioxosulfonyl,anthraquinonesulfonyl. Any of R⁶, R⁷ may carry one or more substituentssuch as halogen, nitro, amino, alkoxy, alkyl, haloalkoxy, alkenyloxy,haloalkenyloxy, alkoxyalkoxy, alkoxyalkylthio, cyano, aminocarbonyloxy,alkylaminocarbonyloxy or dialkylaminocarbonyloxy, acylamino,alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonylor hydroxycarbonyl (but when one of R⁶, R⁷ is connected to the nitrogenof formula III by an oxygen or sulfur atom, then the other of R⁶, R⁷ isH or a group connected to that nitrogen by a carbon-nitrogen linkage ora salt-forming group, such as indicated below). R⁶ and R⁷ may togethercomprise a divalent group, such as an alkylene or haloalkylene oralkyloxyalkylene group or thioether, or its corresponding sulfine orsulfone, (e.g. such that NR.sup. 6 R⁷ together comprise a pyrrolidino,piperidino, morpholino, or thiazolidino ring), any of which may alsocarry a carboxylic ester or amide substituent. The salt-forming group(e.g. when R⁶ is alkylsulfonyl, cycloalkylsulfonyl or arylsulfonyl) maybe a metal (e.g. Na, K or Ca) or ammonium (e.g. NH₄ or loweralkyl-substituted ammonium). R⁶ and R⁷ may comprise a divalent groupsuch that NR⁶ R⁷ together constitute, for instance, a saccharin ringstructure, e.g. ##STR6## which is an active herbicide (such as compoundC62 below) and which upon hydrolysis, can lead to other activeherbicides such as compounds C58 and C59.

Compound C62 for example is obtainable by reaction of saccharin ##STR7##with the appropriate acid chloride.

In this (Formula III) aspect of the invention, X, Y and R¹ may be asdefined above for Formula I, and R² may be as defined above for FormulaII. It is preferred that R¹ be methyl and R² be CHF₂ and particularlythat X be chlorine or (more preferably) fluorine and Y be chlorine.

Representative compounds according to this aspect of the invention areshown in Table 5 below.

Still another aspect of this invention relates to herbicidal compoundsof the formula ##STR8## where --OR⁹ is the residue of an oxime, such asa ketoxime of the formula ##STR9## each alkyl group preferably beinglower alkyl such as methyl. X, Y, R¹ and R² have the meanings given inconnection with Formula I (for X, Y and R¹) and Formula II (for R²).Preferably X is chlorine or (more preferably) fluorine, Y is chlorine,R¹ is methyl and R² is CHF₂ ; in some typical compounds of this kind theradical OR³ COOR⁹ is ##STR10## X is fluorine, Y is chlorine, R¹ ismethyl and R² is CHF₂ ; other typical compounds are identical with thoseexcept that Y is Br or CF₃. Compounds of Formula IV may be prepared byreacting the corresponding acid chloride (i.e. the compound in which thesubstituent at the 5-position of the benzene ring is --OR³ COCl) withthe corresponding oxime in the presence of an acceptor for HCl such astriethylamine or sodium carbonate or sodium hydroxide.

In each aspect of the invention, it is often preferable that any alkyl,alkenyl, alkynyl or alkylene radical have less than 6 carbon atoms.

The compounds of this invention may be prepared by methods generallydescribed in the literature or by methods analogous or similar theretoand within the skill of the art. One type of method starts with anintermediate in which the substituent para to "X" is hydroxyl. Forinstance, one may use the intermediate described in "Synthetic ProcessExample 6" of UK patent application No. GB 2 090 250 published July 7,1982, in which X and Y are Cl, R¹ is CH₃ and R² is CHF₂ (thecorresponding compound in which R² is CH₂ F is made by substitutingchlorofluoromethane for the chlorodifluoromethane used in "SyntheticProcess Example 1" of that published patent application). The OH groupof the intermediate may then be converted to the desired substituent, asby a conventional etherification reaction, e.g., by reacting it with theappropriate bromide in the presence of a known acceptor of HBr such asNaH or a mixture of K₂ CO₃ and NaI.

As illustrated in Examples 2 and 3 below, the synthesis may employ asubstituted phenylhydrazine, whose hydrazine portion is then modified toform a triazolinone ring. Such modification (which in Examples 2 and 3is effected by reaction with pyruvic acid and then with a phosphorylazide) may also be effected by other techniques, such as by treating thesubstituted phenylhydrazine with any of the following four types ofreagents:

(a) an inner salt of a 3-(1-iminoalkylmercapto)-1-propanesulfonic acid(which may be prepared according to Reid and Schmidt, Ann. Chem. 676,114 (1964) from 1,3-propanesultone and a thioamide), to form anamidrazone followed by reaction with a source of phosgene, as by thefollowing reaction sequence (which is also illustrated in Example 15below), ##STR11## in which "Ar" is aromatic as described below.

(b) An imidate ester of the formula ##STR12## to form the correspondingamidrazone (as described, for instance, in the article by Neilson et al"The Chemistry of Amidrazones: Chem. Rev. 70, 151(1970) at page 156),followed by reaction with a source of phosgene, as in (a) above, R^(c)and R^(d) being alkyl or other suitable radical.

(c) A compound of the formula ##STR13## (where R^(a) and R^(b) are loweralkyl) in the presence of a base according to the following sequence:##STR14## in which R¹ is as defined above, e.g. methyl;

(d) A haloalkylnitrile (e.g. a fluoroalkyl, fluorochloroalkyl orfluorobromoalkyl nitrile such as ClCF₂ CN, followed by reaction with asource of phosgene, so that the reaction may proceed along the followinglines, for instance (and as also illustrated in Example 16 below), toform the aryl 3-haloalkyl triazoline, thus: ##STR15##

In Examples 2 and 3 below the "Ar" portion of the aryl hydrazine (whosehydrazine portion is then modified to form the triazoline ring) has halosubstituents at its 2 and 4 positions and an alkoxy group at its 5position. Instead, in each of the processes illustrated above (and inthe process of those Examples 2 and 3), the Ar group may be a phenylradical or a fluorophenyl (e.g. 2-fluorophenyl) or a nitrophenyl (e.g.3-nitrophenyl)alkoxyphenyl (e.g. 3-methoxyphenyl) or, most preferably,halonitrophenyl, particularly a fluoronitrophenyl (such as2-fluoro-5-nitrophenyl) or haloalkoxyphenyl (such as2-fluoro-5-alkoxyphenyl) and the aryl triazoline may then be treated to(a) alkylate the nitrogen at the 4-position of the triazoline ring (inknown manner, e.g. with an alkyl or fluoroalkyl halide, such as withClCHF₂ to add the preferred--CHF₂ substituent) and (b) to introduceadditional substituents onto the aromatic ring, as by halogenation withchlorine or bromine (e.g. by reacting with Cl₂, Br₂ or SO₂ Cl₂). Forinstance the alkylation of the nitrogen at the 4-position may beeffected first, after which the nitro group (if present) may be reducedto an amino group in conventional manner, the amino group may beconverted to a hydroxyl group (as by conventional diazotization) andthen, preferably after etherifying the OH to form an alkoxy (e.g.methoxy) group, the compound may be halogenated as above to place thehalogen substituent or substituents on its benzene ring. The resultingcompound may then be modified at the 5-position of the benzene ring toform the herbicidal compounds of this invention. For instance, formaking the preferred compounds of the invention in which the benzenering has a 2-fluoro substituent, the starting material may be2-fluoro-5-nitrophenylhydrazine, which may be treated as described aboveto produce successively a series of novel compounds such as1-(2-fluoro-5-nitrophenyl)-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one,then1-(2-fluoro-5-nitrophenyl-4,5-dihydro-4-difluoromethyl-3-methyl-1,2,4-triazol-5(1H)-one.These may be converted to the corresponding novel compounds having, atthe 5-position of the benzene ring, successively --NH₂, --OH and(preferably) --OCH₃, followed by halogenation to place, for instance, achloro or bromo substituent at the 4-position of the benzene ring.Instead of alkylating at the 4-position of the ring triazoline at anearly stage, e.g. prior to altering the nitro group, this alkylationstep may be delayed until after the abovedescribed halogenation of thebenzene ring or even until after the conversion of the alkoxy (or other)group at the 5-position of the benzene ring to one of the groupsdescribed at that position in Formulas I, II, III and IV (and Tables 2,3, 4, and 5) above.

Similarly, when the reagent(s) used to react with the aryl hydrazine aresuch as to produce a triazolinone having a haloalkyl (e.g. CHF₂) groupinstead of an alkyl group on the carbon at the 3-position of theheterocyclic ring, the series of new compounds will include,successively, (from 2-fluoro-5-nitrophenyl hydrazine) such compounds as1-(2-fluoro-5-nitrophenyl)-4,5-dihydro-3-difluoromethyl-1,2,4-triazol-5-(1H)-one,then 1-(2-fluoro-5-nitrophenyl)-4,5-dihydro-4-methyl (ordifluoromethyl)-3-difluoromethyl-1,2,4-triazol-5(1H)-one. These may beconverted to the corresponding novel compounds having, at the 5-positionof the benzene ring, successively --NH₂, --OH and (preferably) --OCH₃followed by halogenation to place, for instance, a chloro or bromosubstituent at the 4-position of the benzene ring. When the arylhydrazine is 3-nitrophenyl hydrazine (instead of2-fluoro-5-nitrophenylhydrazine) the series of novel compounds willinclude, successively, such compounds as1-(3-nitrophenyl)-4,5-dihydro-3-difluoromethyl-1,2,4-triazol-5(1H)-one,then 1-(3-nitrophenyl)-4,5-dihydro-4-methyl (ordifluoromethyl)-3-difluoromethyl-1,2,4-triazol-5(1H)-one. These may beconverted to the corresponding novel compounds having, at the 3-positionof the benzene ring, successively --NH₂, --OH and (preferably) --OCH₃,followed by halogenation to place, for instance, chloro or bromosubstituents on the benzene ring.

Example 11 below illustrates a process for making a compound of thisinvention having a sulfonamide group at the 5-position of the benzenering by reacting (a) a compound having an oxypropionic acid substituentat that 5-position with (b) an aryl sulfonylisocyanate.

Another method for introducing the sulfonamide group is by reacting (a)a compound having a phenolic OH group at that 5-position with (b) anN-aryl (or alkyl etc.) sulfonylalkanoic acid amide having a reactiveleaving substituent (e.g. Br, Cl, mesylate or tosylate) on the alkaneportion of the molecule, e.g. ##STR16## Such a reaction can be carriedout in the presence of a base (e.g. in acetone in the presence of sodiumor potassium carbonate). This method is illustrated in Example 14 below.

The following Examples illustrate the preparation of the compounds ofthis invention.

EXAMPLE 1 Ethyl[2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]acetate

To a stirred mixture of 15.0 g (0.048 mole) of1-(2,4-dichloro-5-hydroxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-oneand 3.4 g (0.024 mole) of potassium carbonate in 100 mL of acetone wasadded 8.1 g (0.048 mole) of ethyl bromoacetate. The resultant mixturewas stirred at reflux for three hours. After cooling, the mixture wasevaporated under reduced pressure leaving a residue. This residue waspartitioned between diethyl ether and water. The organic phase waswashed with an aqueous 10% sodium hydroxide solution, then was driedover anhydrous magnesium sulfate and filtered. Evaporation of thefiltrate under reduced pressure produced 17.8 g of a solid. A smallportion of this solid was recrystallized from methanol and water toyield ethyl[2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]acetate(mp 118°-119° C.), compound 17.

The nmr spectrum was consistent with the proposed structure.

The following compounds were also prepared by the process of Example 1from1-(2,4-dichloro-5-hydroxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-b5(1H)-one;1-(4-chloro-2-fluoro-5-hydroxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one;2-[2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]propionicacid, compound A1; or2-[4-chloro-2-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]propionicacid, compound A2, and one of the following:

    ______________________________________                                        Compound       Reagent                                                        ______________________________________                                        14             methyl bromoacetate                                            17             ethyl bromoacetate                                             19             tert-butyl 2-bromopropionate                                   21             tert-butyl bromoacetate                                        22             tert-butyl bromoacetate                                        B6             1-methyl-2-propynyl                                                           2-bromopropionate                                              B7             1,1-dimethyl-2-propynyl                                                       2-chloropropionate                                             B11            bromoacetonitrile                                              B16            α-bromo-γ-butyrolactone                            B22            chloromethyl methylether                                       B23            chloromethyl methylsulfide                                     C1             iodoacetamide                                                  C7             iodoacetamide                                                  C9             N--(1-methylpropyl)                                                           2-bromopropionamide                                            ______________________________________                                    

EXAMPLE 22-[2-Chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]propionicacid

Step A 4-Chloro-2-fluoro-5-methoxyaniline from 2-chloro-4-fluorophenol

The intermediate 4-chloro-2-fluoro-5-methoxyaniline was prepared in afive step synthesis from commercially available 2-chloro-4-fluorophenolas detailed by E. Nagano, et al. in European Patent Application No.69,855.

Step B 4-Chloro-2-fluoro-5-methoxyphenylhydrazine

A stirred solution of 48.0 g (0.27 mole) of4-chloro-2-fluoro-5-methoxyaniline in 500 mL of concentratedhydrochloric acid was cooled to -5° C. and 23.5 g (0.34 mole) of sodiumnitrite in 100 mL of water was added dropwise. After complete additionthe reaction mixture was stirred at 0° C. for one hour. A secondsolution of 154.0 g (0.68 mole) of stannous chloride in 225 mL ofconcentrated hydrochloric acid was cooled to 0° C., and the colddiazonium solution prepared above was added to it slowly. After completeaddition the reaction mixture was allowed to warm to ambienttemperature. The reaction mixture was filtered to collect a solid. Thissolid was dissolved in an aqueous 50% sodium hydroxide solution and thesolution extracted with toluene. The toluene extract was dried withmagnesium sulfate and filtered. The filtrate was concentrated underreduced pressure to yield 22.4 g of4-chloro-2-fluoro-5-methoxyphenylhydrazine as a solid.

The nmr spectrum was consistent with the proposed structure.

Step C Pyruvic acid, 4-chloro-2-fluoro-5-methoxyphenylhydrazone

A stirred solution of 21.0 g (0.11 mole) of4-chloro-2-fluoro-5-methoxyphenylhydrazine and 100 mL of aqueous 10%hydrochloric acid in 100 mL of ethanol was warmed to 40° C., and asolution of 10.0 g (0.114 mole) of pyruvic acid in 20 mL of water wasadded. Upon complete addition the reaction mixture was stirred for onehour. An additional 50 mL of water was added and the reaction mixturefiltered to collect a solid. The solid was air dried to yield 29.0 g ofpyruvic acid, 4-chloro-2-fluoro-5-methoxyphenylhydrazone; mp 166°-169°C.

The nmr spectrum was consistent with the proposed structure.

Step D1-(4-Chloro-2-fluoro-5-methoxyphenyl)-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one

A stirred solution of 27.0 g (0.104 mole) of pyruvic acid,4-chloro-2-fluoro-5-methoxyphenylhydrazone, 29.0 g (0.105 mole) ofdiphenyl phosphoryl azide, and 11.0 g (0.108 mole) of triethylamine in500 mL of toluene was heated under reflux for four hours. The reactionmixture was cooled to ambient temperature and extracted with an aqueous10% sodium hydroxide solution. The extract was neutralized with gaseouscarbon dioxide, and a solid was collected by filtration. The solid wasair dried to yield 11.0 g of1-(4-chloro-2-fluoro-5-methoxyphenyl)-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one;mp 193°-195° C.

The nmr spectrum was consistent with the proposed structure.

Step E1-(4-Chloro-2-fluoro-5-methoxyphenyl)-4,5-dihydro-4-difluoromethyl-3-methyl-1,2,4-triazol-5(1H)-one

A stirred mixture of 10.0 g (0.039 mole) of1-(4-chloro-2-fluoro-5-methoxyphenyl)-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one,10.0 g (0.031 mole) of tetrabutylammonium bromide and 10.0 grams (0.25mole) of sodium hydroxide in 250 mL of cyclohexane was warmed to 60° C.Chlorodifluoromethane (10.0 g, 0.12 mole) was bubbled into the reactionmixture. After complete addition the reaction mixture was warmed toreflux where it stirred for one hour. The hot solution was decanted froma pot residue and cooled to ambient temperature. Methylene chloride wasadded to the cooled mixture to dissolve a solid precipitate. The mixturewas washed with 10% hydrochloric acid then with an aqueous 10% sodiumhydroxide solution. The organic layer was dried with anhydrous magnesiumsulfate and filtered. The filtrate was concentrated under reducedpressure to yield 5.0 g of1-(4-chloro-2-fluoro-5-methoxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one;mp 86°-88° C.

The nmr spectrum was consistent with the proposed structure.

Step F1-(4-Chloro-2-fluoro-5-hydroxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one

A stirred mixture of 4.6 g (0.015 mole) of1-(4-chloro-2-fluoro-5-methoxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-onein 200 mL of methylene chloride was cooled to 10° C. and a solution of11.2 g (0.045) mole of boron tribromide in 45 mL of methylene chloridewas added. Upon complete addition the reaction mixture was stirred forfour hours as it warmed to ambient temperature. After this time 100 mLof water was added, and stirring was continued for an additional 18hours. The organic layer was separated, dried with anhydrous magnesiumsulfate, and filtered. The filtrate was concentrated under reducedpressure to yield 4.4 g of1-(4-chloro-2-fluoro-5-hydroxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one;mp 147°-152° C.

The nmr spectrum was consistent with the proposed structure.

Step G Methyl2-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]propionate

To a stirred mixture of 1.5 g (0.0051 mole) of1-(4-chloro-2-fluoro-5-hydroxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-oneand 0.12 g (0.0051 mole) of sodium hydride in 50 mL ofN,N-dimethylformamide was added 0.85 g (0.0051 mole) of methyl2-bromopropionate. After complete addition the reaction mixture washeated at reflux for two hours, then cooled to room temperature andstirred for approximately 18 hours. The solvent was removed byevaporation under reduced pressure leaving a residue. This residue waspartitioned between diethyl ether and water. The organic phase waswashed with an aqueous 10% sodium hydroxide solution. The organic phasewas dried over anhydrous magnesium sulfate and filtered. The filtratewas evaporated under reduced pressure to yield 1.5 g of methyl2-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]propionateas an oil, Compound 3.

The nmr spectrum was consistent with the proposed structure.

The following compounds were also prepared by the process of Example 2,Step G, from1-(2,4-dichloro-5-hydroxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one;1-(4-chloro-2-fluoro-5-hydroxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one;or compound A2 and one of the following reagents:

    ______________________________________                                        Compound      Reagent                                                         ______________________________________                                        1             methyl bromoacetate                                             2             methyl 2-bromopropionate                                        5             ethyl 2-bromopropionate                                         6             ethyl 2-bromopropionate                                         18            ethyl 4-bromopropionate                                         20            ethyl 2-bromoisobutyrate                                        B21           N,N--diethyl-2-chloroacetamide                                  C8            N,N--diethyl-2-chloroacetamide                                  ______________________________________                                    

Step H2-[2-Chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]propionicacid

A stirred mixture of 1.3 g (0.0034 mole) of methyl2-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]propionateand 1.0 g (0.018 mole) of potassium hydroxide in 15 mL of ethanol and 15mL of water was heated at reflux for three hours. The mixture wasallowed to cool to room temperature and stand for two days. The solventwas evaporated from the mixture leaving a solid. This solid wasdissolved in water, and the solution was made acidic with concentratedhydrochloric acid. This solution was extracted with methylene chloride.The extract was dried over anhydrous magnesium sulfate and filtered.Evaporation of the solvent from the filtrate left 0.85 g of2-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]propionicacid as a solid (mp 50°-55° C.), Compound A2.

Compound A1 was also prepared by the method of Example 2, Step H, fromCompound 2.

EXAMPLE 32-[4-Chloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)-2-methylphenoxy]propionicacid

Step A 4-Methyl-3-methoxyphenylhydrazine

A stirred mixture of 100.0 g (0.73 mole) of 4-methyl-3-methoxyaniline in800 mL of concentrated hydrochloric acid was cooled to -5° C. A solutionof 501.5 g (0.73 mole) of sodium nitrite in 250 mL of water was addedslowly while maintaining the temperature of the reaction mixture below0° C. The resultant mixture was stirred at -5° C. for 30 minutes. A coldsolution of 330.0 g (1.46 mole) of tin (II) chloride dihydrate in 360 mLof concentrated hydrochloric acid was added over one hour. Aftercomplete addition the resultant mixture was allowed to warm to roomtemperature. A solid precipitate formed and was collected by filtrationand stirred in 200 mL of water. This mixture was neutralized with 50%aqueous sodium hydroxide, and extracted with toluene. The extract wasdried over anhydrous magnesium sulfate and filtered. The filtrate wasevaporated under reduced pressure to yield 58.0 g of4-methyl-3-methoxyphenylhydrazine as an oil.

The nmr spectrum was consistent with the proposed structure.

Step B Pyruvic acid, 4-methyl-3-methoxyphenylhydrazone

To a stirred mixture of 57.6 g (0.378 mole) of4-methyl-3-methoxyphenylhydrazine in 400 mL of ethanol and 400 mL of 1Nhydrochloric acid was added 33.3 g (0.0378 mole) of pyruvic acid. Aftercomplete addition the mixture was stirred at room temperature for onehour, and 1 liter of water was added. The mixture was extracted withmethylene chloride. The extract was dried over anhydrous magnesiumsulfate and filtered. The filtrate was evaporated under reduced pressureto yield 59.0 g of pyruvic acid, 4-methyl-3-methoxyphenylhydrazone.

The nmr spectrum was consistent with the proposed structure.

Step C4,5-Dihydro-1-(4-methyl-3-methoxyphenyl)-3-methyl-1,2,4-triazol-5(1H)-one

To a stirred mixture of 56.8 g (0.26 mole) of pyruvic acid,4-methyl-3-methoxyphenylhydrazone in 1500 mL of toluene was added 25.9 g(0.26 mole) of triethylamine. The mixture was heated at 50° C., and 70.3g (0.26 mole) of diphenyl phosphoryl azide was added. The resultantmixture was heated at reflux for approximately 18 hours. The mixture wascooled and extracted with four 200 mL portions of an aqueous 10% sodiumhydroxide solution. The aqueous extracts were combined, washed withtoluene, and made acidic. The resultant solid was collected byfiltration and air dried to yield 75.0 g of4,5-dihydro-1-(4-methyl-3-methoxyphenyl)-3-methyl-1,2,4-triazol-5(1H)-one(mp 164°-168° C.).

The nmr spectrum was consistent with the proposed structure.

Step D4-Difluoromethyl-4,5-dihydro-1-(4-methyl-3-methoxyphenyl)-3-methyl-1,2,4-triazol-5(1H)-one

A stirred mixture of 60.0 g (0.28 mole) of4,5-dihydro-1-(4-methyl-3-methoxyphenyl)-3-methyl-1,2,4-triazol-5(1H)-one,60.0 g (0.19 mole) of tetrabutylammonium bromide and 60.0 g (1.5 mole)of powdered sodium hydroxide in 2 liters of cyclohexane was heated atreflux. During a two hour period 60.0 g (0.67 mole) of gaseousdifluorochloromethane was bubbled into the mixture. After completeaddition the mixture was stirred at reflux for one hour, then allowed tocool to 70° C. The supernatant liquid was decanted and washed withaqueous 10% hydrochloric acid followed by an aqueous 10% sodiumhydroxide solution. The organic layer was dried with magnesium sulfateand filtered. The filtrate was evaporated under reduced pressure toleave a solid. This solid was triturated with petroleum ether andfiltered. The filter cake was air dried to yield 18.5 g of4-difluoromethyl-4,5-dihydro-1-(4-methyl-3-methoxyphenyl)-3-methyl-1,2,4-triazol-5-(1H)-one.

The nmr spectrum was consistent with the proposed structure.

Step E1-(2-Chloro-4-methyl-5-methoxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one

A solution of 15.0 g (0.056 mole) of4-difluoromethyl-4,5-dihydro-1-(4-methyl-3-methoxyphenyl)-3-methyl-1,2,4-triazol-5(1H)-oneand 7.5 g (0.056 mole) of sulfuryl chloride in 100 mL of chloroform wasstirred at room temperature for two hours. The reaction mixture wasconcentrated under reduced pressure to leave a residue. This residue wasdissolved in methylene chloride and washed with an aqueous 10% sodiumhydroxide solution. The organic layer was dried with magnesium sulfateand filtered. The filtrate was concentrated under reduced pressure toyield 16.5 g of1-(2-chloro-4-methyl-5-methoxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-oneas a solid.

The nmr spectrum was consistent with the proposed structure.

Step F1-(2-Chloro-4-methyl-5-hydroxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one

To a stirred solution of 16.0 g (0.053 mole) of1-(2-chloro-4-methyl-5-methoxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-onein 100 mL of methylene chloride at 10° C. was added dropwise 39.6 g(0.16 mole) of boron tribromide. The resultant mixture was stirred atroom temperature for two days. This mixture was washed with 100 mL ofwater. The organic layer was dried with anhydrous magnesium sulfate andfiltered. The filtrate was concentrated under reduced pressure to leavean oil. This oil was stirred in petroleum ether:diethyl ether (90:10)forming a solid. The solid was collected by filtration to yield 10.5 gof1-(2-chloro-4-methyl-5-hydroxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one(mp 154°-156° C.).

The nmr spectrum was consistent with the proposed structure.

Step G Methyl2-[4-chloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)-2-methylphenoxy]propionate

In a manner similar to Example 2, Step G, the reaction of 3.0 g (0.01mole) of1-(2-chloro-4-methyl-5-hydroxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one,0.25 g (0.01 mole) of sodium hydride and 1.75 g (0.01 mole) of methyl2-bromopropionate in 100 mL of N,N-dimethylformamide produced 3.7 g ofmethyl2-[4-chloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)-2-methylphenoxy]propionateas an oil, Compound 4.

The nmr spectrum was consistent with the proposed structure.

Compound 7 was prepared by the process described for Compound 4, butusing ethyl 2-bromopropionate in Step G.

Step H2-[4-Chloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)-2-methylphenoxy]propionicacid

In a manner similar to Example 2, Step H, the reaction of 3.3 g (0.0088mole) of methyl2-[4-chloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)-2-methylphenoxy]propionatewith 1.5 g (0.27 mole) of potassium hydroxide in 50 mL of ethanol and 15mL of water produced 2.7 g of2-[4-chloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)-2-methylphenoxy]propionicacid as a solid (mp 56°-60° C.), Compound A3.

The nmr spectrum was consistent with the proposed structure.

EXAMPLE 4

2-Nitropropyl2-[2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]propionate

A stirred mixture of 0.5 g (0.0013 mole) of2-[2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]propionicacid (Compound A1), 1.0 g (0.0095 mole) of 2-nitro-1-propanol and 0.05 g(0.0003 mole) of p-toluenesulfonic acid monohydrate in 60 mL of toluenewas heated at reflux. The water generated in the reaction was removed bycollection in a Dean-Stark trap. After refluxing for a total of twohours, the solvent was removed by distillation under reduced pressureleaving a residue. This residue was dissolved in diethyl ether andwashed first with water then with an aqueous 10% sodium hydroxidesolution. The organic phase was dried over anhydrous magnesium sulfateand filtered. The filtrate was evaporated to yield 0.5 g of2-nitropropyl2-[2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]propionateas an oil, Compound B1.

The nmr spectrum was consistent with the proposed structure.

Compound 11 was also prepared by the method of Example 4 from CompoundA1 and n-butanol.

EXAMPLE 5 2-Propenyl2-[2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]propionate

Under a dry nitrogen atmosphere, a stirred solution of 0.5 g (0.0013mole) of methyl2-[2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]propionate(Compound 2) and approximately 0.01 g of sodium methoxide in 30 mL of2-propen-1-ol was heated at reflux. After approximately 5 mL of methanolwas collected in a Dean-Stark trap, the reaction mixture was cooledslightly, and the remaining solvent removed by distillation underreduced pressure leaving a residue. This residue was dissolved indiethyl ether and washed with water. The organic phase was dried overanhydrous magnesium sulfate and filtered. The filtrate was evaporatedunder reduced pressure to yield 0.55 g of 2-propenyl2-[2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]propionateas an oil, Compound B2.

The nmr spectrum was consistent with the proposed structure.

Analysis Calc'd for C₁₆ H₁₅ N₃ Cl₂ F₂ O₄ : C 45.52;H 3.58;N 9.95. Found:C 45.24;H 3.76;N 9.87.

The following compounds were also prepared by the process of Example 5from1-(2,4-dichloro-5-hydroxyphenyl)-4-difluromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one;compound A1; or compound A2 and the following reagents:

    ______________________________________                                        Compound          Reagent                                                     ______________________________________                                         9                n-propanol                                                  10                2-propanol                                                  15                n-propanol                                                  16                2-propanol                                                  B3                2-propyn-1-ol                                               B5                2-methoxyethanol                                            ______________________________________                                    

EXAMPLE 6N-methylsulfonyl-2-[2,4-Dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]propionamide

Step A2-[2,4-Dichloro-5-(4-difluromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]-propionylchloride

A stirred mixture of 2.9 g (0.0075 mole) of2-[2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]propionicacid (Compound A-1) in 5 mL of thionyl chloride was heated at reflux for1.5 hours. The mixture was cooled, and the excess thionyl chloride wasremoved by evaporation under reduced pressure, leaving 3.1 g of productas an oil.

Step BN-Methylsulfonyl-2-[2,4-dichloro-5-(4-difluoro-methyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]propionamide

A mixture of 0.56 g of the oil from Step A and 0.56 g (0.0059 mole) ofmethanesulfonamide was heated at 80° C. for 3.5 hours. The mixture wascooled and diluted with water, forming a gummy precipitate. The waterwas decanted, and the residue was partitioned between water andmethylene chloride. The organic phase was washed with three 100 mlportions of water, dried over anhydrous magnesium sulfate, and filtered.The filtrate was evaporated under reduced pressure to leave a tan solidwhich was dissolved in 30 mL of 1N sodium hydroxide and 50 mL of water.The basic mixture was filtered, and the filtrate was made acidic withconcentrated hydrochloric acid. A precipitate formed and was collectedby filtration. The filter cake was washed with water and dried to yield0.34 g ofN-methylsulfonyl-2-[2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]propionamide(mp 185°-188° C.), Compound C3.

The nmr spectrum was consistent with the proposed structure.

Analysis Calc'd for C₁₄ H₁₄ Cl₂ F₂ N₄ O₅ S: C 36.61; H 3.07; N 12.20.Found: C 36.79; H 3.01; N 12.41.

Compounds C4, C5 and C6 were prepared by the process described inExample 6 using trifluoromethanesulfonamide, ammonia and methylaminerespectively in Step B. Compounds C2 and C18 were prepared by the methodof Example 6 from Compound A2, using methylamine and methanesulfonamiderespectively in Step B.

EXAMPLE 7 Ethyl2-[2,4-dibromo-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]propionate

Step A1-(2,4-Dibromo-5-methoxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one

To a stirred mixture of 12.0 g (0.047 mole) of1-(3-methoxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one(prepared from 3-methoxyaniline using the method of Example 2, StepsB-E) in 75 mL of acetic acid was added 30.0 g (0.19 mole) of bromine.The mixture was heated at reflux for six hours, then cooled. The solventwas removed by distillation, leaving a residue. This residue wasdissolved in diethyl ether, and the resultant solution was washed firstwith an aqueous 10% sodium thiosulfate solution followed by water. Theorganic solution was dried over anhydrous magnesium sulfate andfiltered. The filtrate was evaporated under reduced pressure, leaving asolid. This solid was triturated in petroleum ether and filtered toyield 17.4 g of1-(2,4-dibromo-5-methoxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one.

The nmr spectrum was consistent with the proposed structure.

Step B1-(2,4-Dibromo-5-hydroxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one

A mixture of 17.2 g (0.042 mole) of1-(2,4-dibromo-5-methoxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5-(1H)-oneand 50.6 g (0.020 mole) of boron tribromide in 100 mL of methylenechloride was stirred at room temperature for 18 hours. The mixture waswashed with 50 mL of water, and the organic phase was dried overanhydrous magnesium sulfate. This mixture was filtered, and the filtratewas evaporated under reduced pressure to yield 16.1 g of1-(2,4-dibromo-5-hydroxyphenyl)4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5-(1H)-oneas a solid.

The nmr spectrum was consistent with the proposed structure.

Step C Ethyl2-[2,4-dibromo-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)-phenoxy]propionate

To a stirred solution of 1.25 g (0.0031 mole) of1-(2,4-dibromo-5-hydroxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-onein 60 mL of N,N-dimethylformamide was added 0.57 g (0.0033 mole) ofethyl 2-bromopropionate. The resultant mixture was heated at 130° . fortwo hours, then was cooled. The solvent was evaporated from the mixtureunder reduced pressure, leaving a solid. This solid was dissolved indiethyl ether, and the solution was washed first with water, then withan aqueous 10% sodium hydroxide solution. The organic solution was driedover anhydrous magnesium sulfate and filtered. The filtrate wasevaporated under reduced pressure to yield 1.0 g of ethyl2-[2,4-dibromo-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]propionateas an oil, Compound 8.

The nmr spectrum was consistent with the proposed structure.

EXAMPLE 8 1-Methylpropyl2-[2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]propionate

To a stirred solution of 1.0 g (0.0025 mole) of2-[2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazoll-yl)phenoxy]propionylchloride (prepared in Example 6, Step A) in 15 mL of sec-butanol wasadded 0.27 g (0.0027 mole) of triethylamine. The reaction mixture wasstirred at room temperature for 20 minutes, then heated at 70° C. for11/2 hours. The mixture was allowed to cool and was stirred at roomtemperature for approximately 18 hours. The solvent was removed byevaporation under reduced pressure, leaving a residue which waspartitioned between deithyl ether and water. The organic phase waswashed in succession with water, an aqueous 10% sodium hydroxidesolution, water, aqueous 10% hydrochloric acid, a saturated aqueoussodium bicarbonate solution, and water. The organic phase was dried overanhydrous magnesium sulfate, then filtered. The filtrate was evaporatedunder reduced pressure to yield 0.42 g of 1-methylpropyl1-[2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)-phenoxy]propionate asan oil, Compound 12.

The nmr spectrum was consistent with the proposed structure.

Compound B4 was also prepared by the method of Example 8 from the acidchloride of Compound A2 and 2-propyn-1-ol.

EXAMPLE 9 Ethyl[2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]fluoroacetate

To a stirred mixture of 2.0 g (0.0065 mole) of1-(2,4-dichloro-5-hydroxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-oneand 0.91 g (0.0065 mole) of ethyl chlorofluoroacetate in 50 mL ofethanol was added a solution of 0.15 g (0.0065 mole) of sodium in 5 mLof ethanol. The reaction mixture was heated at reflux for 34 hours. Themixture was cooled, and the solvent was removed by evaporation underreduced pressure, leaving a residue. This residue was dissolved indiethyl ether, and the solution was washed first with water, followed byan aqueous 10% sodium hydroxide solution. The organic phase was driedover anhydrous magnesium sulfate, then filtered. The filtrate wasevaporated under reduced pressure to yield 0.95 g of ethyl[2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]fluroacetateas an oil, Compound 51.

The nmr spectrum was consistent with the proposed structure.

EXAMPLE 10 Ethyl2-[2,4-dichloro-5-(4-fluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]propionate

Step A1-[2,4-Dichloro-5-(1-methylethoxy)phenyl]-4-fluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one

A solution of 6.0 g (0.020 mole) of1-[2,4-dichloro-5-(1-methylethoxy)phenyl]-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-onein 45 mL of N,N-dimethylformamide was added to 0.55 g (0.022 mole) ofsodium hydride in 30 mL of N,N-dimethylformamide. The reaction mixturewas stirred at room temperature for 15 minutes.

Chlorofluoromethane was added dropwise to the stirred reaction mixtureby condensing the gas on a dry ice condenser. During the addition themixture was heated slowly to 60° C. at which point the mixture began toreflux. The addition of chlorofluromethane was discontinued, and thereaction mixture was allowed to cool to room temperature and stand forapproximately 18 hours. Heating at reflux was resumed, and an additionalamount of chlorofluoromethane was added during a ten minute period.After complete addition, the reaction mixture was heated at reflux forone hour, then allowed to cool. The solvent was removed by distillationunder reduced pressure, leaving a residue. This residue was partitionedbetween diethyl ether and water. The organic phase was washed first with1N sodium hydroxide, then water. The organic solution was dried overanhydrous magnesium sulfate and filtered. The filtrate was evaporatedunder reduced pressure to yield 3.8 g of1-[2,4-dichloro-5-(1-methylethoxy)phenyl]-4-fluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-oneas an oil.

The nmr spectrum was consistent with the proposed structure.

Step B1-(2,4-Dichloro-5-hydroxyphenyl)-4-fluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one

To 5 mL of stirring concentrated sulfuric acid was added portionwise0.53 g (0.0016 mole) of1-[2,4-dichloro-5-(1-methylethoxy)phenyl]-4-fluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one.After complete addition, the mixture was stirred at room temperature for2.5 hours. The mixture was poured into 100 mL of ice water and stirredfor 30 minutes. The aqueous mixture was extracted with diethyl ether,and the extract was washed with water. The organic phase was dried overanhydrous magnesium sulfate and filtered. The filtrate was evaporatedunder reduced pressure to yield 0.34 g of1-(2,4-dichloro-5-hydroxyphenyl)-4-fluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-oneas a solid.

The nmr spectrum was consistent with the proposed structure.

This reaction was repeated using 2.8 g of1-[2,4-dichloro-5-(1-methylethoxy]-4-fluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one,producing an additional 1.9 g of product.

Step C Ethyl2-[2,4-dichloro-5-(4-fluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)-phenoxy]propionate

A mixture of 0.56 g (0.0019 mole) of1-(2,4-dichloro-5-hydroxyphenyl)-4-fluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-oneand 1.1 g (0.0076 mole) of anhydrous potassium carbonate in 15 mL ofacetone was stirred for 15 minutes. Sodium iodide (approximately 0.01 g)and 0.37 g (0.002 mole) of ethyl 2-bromopropionate were added, and theresultant mixture was heated at reflux for 1.5 hours. The mixture wascooled and filtered. The filtrate was evaporated under reduced pressure,leaving a residue. This residue was partitioned between diethyl etherand water. The organic phase was washed with water, dried over anhydrousmagnesium sulfate, and filtered. The filtrate was evaporated underreduced pressure, leaving an oil. This oil was stirred in n-pentane, andthe supernant was decanted, leaving an oily residue. The oil was driedat 70° C. under a stream of nitrogen to yield 0.70 g of ethyl2-[2,4-dichloro-5-(4-fluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]propionate,Compound 13.

The nmr spectrum was consistent with the proposed structure.

EXAMPLE 11N-(4-Methylphenylsulfonyl)-2-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]propionamide

A stirred mixture of 0.78 g (0.0021 mole) of2-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]propionicacid, 0.42 g (0.0021 mole) of p-toluenesulfonyl isocyanate and 0.05 g(0.0004 mole) of 4-dimethylaminopyridine in 50 mL of toluene was heatedat reflux for approximately 18 hours. The mixture was allowed to cool toroom temperature and was stirred for 24 hours. The solvent was removedby evaporation at reduced pressure to leave a residue. This residue waspurified by column chromatography on silica gel, eluting withtoluene:ethyl acetate (1:1). The appropriate fractions were combined andevaporated under reduced pressure to yield 0.7 g ofN-(4-methylphenylsulfonyl)-2-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]propionamideas a solid, Compound C10.

The nmr spectrum was consistent with the proposed structure.

Compound C25 was prepared by the method of Example 11 using2-chlorobenzenesulfonyl isocyanate.

Example 122-[2-Chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]propionic acid, sodium salt.

A mixture of 1.0 g (0.0027 mole) of2-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]propionicacid and 0.07 g (0.0027 mole) of sodium hydride in 30 mL oftetrahydrofuran was stirred at room temperature for approximately 18hours. The solvent was removed by evaporation to yield 0.9 g of2-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]propionic acid, sodium salt as a solid, Compound A4.

Compounds C19 and C20 were prepared by the method of Example 12 fromcompounds C18 and C10 respectively. Compound A6 was prepared by a methodanalogous to that of Example 12 from Compound A2, substitutingisopropylamine for sodium hydride.

Example 13[2,4-Dichloro-5-(3-difluoromethyl-4,5-dihydro-4-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]acetamide

Step A Ethyl difluoroacetylcarbamate

During a 30 minute period 65.4 g (0.55 mole) of thionyl chloride wasadded to 50.0 g (0.52 mole) of difluoroacetic acid while stirring. Gasevolved during the addition was returned to the reaction mixture bycondensation on a dry ice condenser. After complete addition, themixture was stirred at room temperature for approximately two hours.Urethane, 46.4 g (0.52 mole), was added and, after complete addition,the reaction mixture was heated at 60°-70° C. for three hours. Themixture was cooled to room temperature and stirred for approximately 18hours. The mixture was heated at about 75° C. for two hours, thencooled. The mixture was evaporated under reduced pressure to leave anoily residue. This residue crystallized upon standing. The crystallizedresidue was washed with petroleum ether and filtered to yield 68.4 g ofethyl difluoroacetylcarbamate (mp 55°-57° C.).

Step B1-[2,4-Dichloro-5-(1-methylethoxy)phenyl]-3-difluoromethyl-4,5-dihydro-1,2,4-triazol-5(1H)-one

To a stirred solution of 11.8 g (0.05 mole) of2,4-dichloro-5-(1-methylethoxy)phenylhydrazine and 10.0 g (0.06 mole) ofethyl difluoroacetylcarbamate in 130 mL of xylene was added 2.5 g (0.02mole) of phosphorus pentoxide. After complete addition the mixture washeated at reflux for 1.5 hours then allowed to cool to room temperaturefor approximately 18 hours. The reaction mixture was decanted from adark residue in the reaction flask and washed with water. The washedmixture was extracted with a 10% aqueous sodium hydroxide solution. Thebasic extract was made acidic with concentrated hydrochloric acid toform an oily precipitate. This aqueous phase was decanted from the oilyresidue and fresh water added to wash the residue. This residue wasdissolved in 160 mL of methylene chloride and filtered through a celitepad. The filtrate was dried over anhydrous magnesium sulfate andfiltered. The filtrate was evaporated under reduced pressure to leave asemi-solid residue. The residue was triturated with approximately 125 mLof petroleum ether to provide 8.2 g of1-[2,4-dichloro-5-(1-methylethoxy)phenyl]-3-difluoromethyl-4,5-dihydro-1,2,4-triazol-5(1H)-one.

Step C1-[2,4-Dichloro-5-(1-methylethoxy)phenyl]-3-difluoromethyl-4,5-dihydro-4-methyl-1,2,4-triazol-5(1H)-one.

A stirred mixture of 4.0 g (0.012 mole) of1-[2,4-dichloro-5-(1-methylethoxy)phenyl]-3-difluoromethyl-4,5-dihydro-1,2,4-triazol-5(1H)-oneand 4.1 g (0.03 mole) of potassium carbonate in 160 mL of acetone washeated at reflux for 0.5 hours then cooled to about 50° C. Methyliodide, 8.4 g (0.06 mole), was added and the mixture stirred at 45° forone hour then at reflux for one hour. The mixture was cooled to roomtemperature and evaporated under reduced pressure to leave an oil. Thisoil was partitioned between methylene chloride and water. The organicphase was washed with a 10% aqueous sodium hydroxide solution and thendried over anhydrous magnesium sulfate. The mixture was filtered and thefiltrate evaporated under reduced pressure to leave an oil. This oilsolidified when stirred with petroleum ether and upon filtrationprovided 2.6 g of1-[2,4-dichloro-5-(1-methylethoxy)phenyl]-3-difluoromethyl-4,5-dihydro-4-methyl-1,2,4-triazol-5-(1H)-one (mp 95°-97° C).

Step D1-(2,4-Dichloro-5-hydroxyphenyl)-3-difluoromethyl-4,5-dihydro-4-methyl-1,2,4-triazol-5(1H)-one

Hydrolysis of 2.2 g (0.0063 mole) of1-[2,4-dichloro-5-(1-methylethoxy)phenyl]-3-difluoromethyl-4,5-dihydro-4-methyl-1,2,4-triazol-5(1H)-onein 5 mL of concentrated sulfuric acid produced 1.4 g of1-(2,4-dichloro-5-hydroxyphenyl)-3-difluoromethyl-4,5-dihydro-4-methyl-1,2,4-triazol-5(1H)-one(mp 176°-179° C.).

Step E[2,4-Dichloro-5-(3-difluoromethyl-4,5-dihydro-4-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]acetamide

In a manner similar to Example 1, the reaction of 0.72 g (0.00023 mole)of1-(2,4-dichloro-5-hydroxyphenyl)-3-difluromethyl-4,5-dihydro-4-methyl-1,2,4-triazol-5(1H)-one,0.32 g (0.00023 mole) of potassium carbonate, and 0.47 g (0.00025 mole)of iodoacetamide in 5 mL of acetone produced 0.69 g of[2,4-dichloro-5-(3-difluoromethyl-4,5-dihydro-4-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]acetamide(mp 190°-193.5° C).

The nmr spectrum was consistent with the proposed structure.

The following compounds were prepared by the process of S.Chandrasekaran et al., Synthetic Communications, 12(9), 727-731 (1982)from Compound A2 and the following reagents.

    ______________________________________                                        Compound   Reagent                                                            ______________________________________                                        B8         tetrahydrofurfuryl alcohol                                         B9         methyl hydroxyacetate                                              B10        2-methyl-3,3,4,4-tetrafluoro-2-butanol                             B12        furfuryl alcohol                                                   B13        N,N--dimethylethanolamine                                          B14        3-hydroxytetrahydrofuran                                           B15        phenol                                                             B17        ethanethiol                                                        B18        ethyl 2-mercaptoacetate                                            B30        trifluoroethanol                                                   B31        acetone cyanohydrin                                                B32        benzyl alcohol                                                     B33        2-propanethiol                                                     C11        O,N--dimethylhydroxylamine hydrochloride                           C12        (2-propynyl)amine                                                  C13        aniline                                                            C14        dimethylamine                                                      C15        diethylamine                                                       C16        ethylamine hydrochloride                                           C17        glycine methyl ester hydrochloride                                 C22        2-amino-2-methylpropionitrile                                      C23        N--methylaniline                                                   ______________________________________                                    

Compound B25 was prepared by the method of Lonord et al., J. Org. Chem.27,282-284 (1962) from Compound B23.

Compound A5 was prepared by the hydrolysis of Compound 22 using theprocedure described by Kurtev et al., Synthesis (1975), 106-108.

Characterizing properties of some of the compounds of the invention aregiven in Table 6 below.

Example 14N-(2,5-dimethoxyphenylsulfonyl)-2-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]propionamide

Step A 2,5-Dimethoxyphenylsulfonamide

To a stirred solution of 15.0 g (0.063 mole) of2,5-dimethoxybenzenesulfonyl chloride in 150 mL of tetrahydrofuran wasadded dropwise 80 mL of ammonia (28% aqueous solution). After completeaddition the mixture was allowed to stir for 1.75 hours at roomtemperature. Upon standing the mixture separated into two phases. Theorganic phase was removed from the aqueous phase and was evaporatedunder reduced pressure to leave a solid residue. This residue wasrecrystallized from hot water (125 mL) and ethanol (40 mL) to yield 13.1g of 2,5-dimethoxyphenylsulfonamide (mp 146.5-148.5).

The nmr spectrum was consistent with the proposed structure.

Step B N-(2,5-Dimethoxyphenylsulfonyl)-2-bromo-propionamide

A stirred mixture of 7.0 g (0.032 mole) of2,5-dimethoxyphenylsulfonamide in 10 mL of 2-bromopropionyl chloride washeated at reflux for 40 minutes then allowed to cool to roomtemperature. The resultant solution was poured into petroleum ether.Crystals formed after scratching the sides of the flask and werecollected by filtration. The filter cake was washed four times withfresh petroleum ether to yield 10.3 g ofN-(2,5-dimethoxyphenylsulfonyl)-2-bromopropionamide (mp 116°-118° C.).

The nmr spectrum was consistent with the proposed structure.

Step CN-(2.5-Dimethoxyphenylsulfonyl)-2-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]propionamide

To a stirred solution of 0.75 g (0.0026 mole) of1-(4-chloro-2-fluoro-5-hydroxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-oneand 0.89 g (0.0026 mole) ofN-(2,5-dimethoxyphenylsulfonyl)-2-bromopropionamide in 50 mL of acetonewas added 1.04 g (0.0026 mole) of potassium carbonate. After completeaddition the mixture was heated at 45° C. for two days. The resultantmixture was cooled and the solvent was removed by evaporation underreduced pressure to leave a residue. The residue was dissolved in 100 mLof water. The aqueous solution was acidified by the dropwise addition ofconcentrated hydrochloric acid producing a precipitate. The precipitatewas collected by filtration. The filter cake was washed with water andthen dried under reduced pressure to leave 1.23 g ofN-(2,5-dimethoxyphenylsulfonyl)-2-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]propionamide(mp 168°-172° C.) Compound C90.

The nmr spectrum was consistent with the proposed structure.

EXAMPLE 151-(4-Chloro-2-fluoro-5-methoxyphenyl)-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-oneas an intermediate

Step A N'-(4-Chloro-2-fluoro-5-methoxyphenyl)acetamidrazone

A stirred mixture of 1.91 g (0.01 mole) of4-chloro-2-fluoro-5-methoxyphenylhydrazine and 1.97 g (0.01 mole) of3-(1-iminoethylmercapto)-1-propanesulfonic acid, inner salt, (preparedby the method of Reid et al, Ann. Chem. 676, 114 (1964)) in 50 mL ofanhydrous ethanol was heated at reflux for 1.25 hours. The mixture wascooled and evaporated under reduced pressure to leave 3.96 g of aresidue. A portion of this residue, 3.33 g, was dissolved in 50 mL ofwater. The resultant cloudy solution was filtered through a pad ofcelite and the filtrate was extracted with methylene chloride. Theclarified aqueous solution was basified with approximately 8 mL of anaqueous 10% sodium hydroxide solution. An oil precipitated from thebasic mixture and slowly solidified. This solid was collected byfiltration. The filter cake was washed with water to yield 1.31 g ofN'-(4-chloro-2-fluoro-5-methoxyphenyl)acetamidrazone (mp 106°-107° C.).

The nmr analysis was consistent with the proposed structure.

Analysis calc'd for C₉ H₁₁ ClFN₃ O: C 46.66, H 4.79, N 18.14. Found: C46.10, H 4.81, N 17.70.

Step B1-(4-Chloro-2-fluoro-5-methoxyphenyl)-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one

A solution of 1.71 g (0.0086 mole) of trichloromethyl chloroformate in 5mL of toluene was added dropwise to a stirred solution of 1.0 g (0.0043mole) of N'-(4-chloro-2-fluoro-5-methoxyphenyl)acetamidrazone in 50 mLof toluene. After complete addition the mixture was stirred at roomtemperature for five minutes then was heated slowly until a slow refluxwas obtained. Reflux was maintained for approximately 15 minutes. Themixture was cooled and evaporated under reduced pressure to leave 1.22 gof a solid. Approximately 1.0 g of this solid was dissolved in 100 mL ofmethylene chloride. The resultant solution was filtered and the filtratewas extracted with three 25 mL portions of an aqueous 10% sodiumhydroxide solution followed by three 25 mL portions of 1N sodiumhydroxide. Each set of three similar extracts were combined and washedwith methylene chloride. Both of the washed extracts were acidified withconcentrated hydrochloric acid producing a precipitate from each. Thesolids were collected by filtration to provide 0.3 g and 0.12 g, fromthe 10% and 1N base solutions respectively, of1-(4-chloro-2-fluoro-5-methoxyphenyl)-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one(mp 209°-211° C.).

The nmr spectrum was consistent with the proposed structure.

EXAMPLE 161-(2,4-Dichloro-5-hydroxyphenyl)-3-chlorodifluoromethyl-4,5-dihydro-4-methyl-1,2,4-triazol-5(1H)-oneas an intermediate

Step AN'-[2,4-Dichloro-5-(1-methylethoxy)phenyl]chlorodifluoroacetamidrazone

A stirred solution of 9.4 g (0.04 mole) of2,4-dichloro-5-(1-methylethoxy)phenylhydrazine in 350 mL of absolutemethanol was cooled to 0°. Gaseous chlorodifluoroacetonitrile (8.0 g,0.07 mole) was added to the mixture. After complete addition the mixturewas allowed to warm to room temperature and stir for 3.5 hours. Thestirring was stopped and the mixture stood at room temperature for twodays. The solvent was evaporated for the mixture under reduced pressureto leave 13.86 g ofN'-[2,4-dichloro-5-(1-methylethoxy)phenyl]chlorodifluoroacetamidrazoneas an oily residue

Step B1-[2,4-Dichloro-5-(1-methylethoxy)phenyl]-3-chlorodifluoromethyl-4,5-dihydro-1,2,4-triazol-5(1H)-one

In a manner similar to Example 15, Step B, the reaction of 13.86 g ofthe oily residue from Step A plus 2.7 g of similar material prepared ina separate experiment and 19.87 g (0.1 mole) of trichloromethylchloroformate in 600 mL of toluene produced 5.4 g of1-[2,4-dichloro-5-(1-methylethoxy)phenyl]-3-chlorodifluoromethyl-4,5-dihydro-1,2,4-triazol-5(1H)-one(mp 115°-119° C.).

The nmr spectrum was consistent with the proposed structure.

Step C1-[2,4-Dichloro-5-(1-methylethoxy)phenyl]-3-chlorodifluoromethyl-4,5-dihydro-4-methyl-1,2,4-triazol-5(1H)-one

In a manner similar to Example 13, Step C, the reaction of 4.0 g (0.011mole) of1-[2,4-dichloro-5-(1-methylethoxy)phenyl]-3-chlorodifluoromethyl-4,5-dihydro-1,2,4-triazol-5(1H)-one,4.26 g (0.03 mole) of methyl iodide, and 2.07 g (0.015 mole) ofpotassium carbonate in 40 mL of acetone provided 3.74 g of1-[2,4-dichloro-5-(1-methylethoxy)phenyl]-3-chlorodifluoromethyl-4,5-dihydro-4-methyl-1,2,4-triazol-5(1H)-oneas a solid. Recrystallization of a small portion of this solid fromethanol and water provided a pale yellow solid, mp 69°-72° C.

The nmr spectrum was consistent with the proposed structure.

Analysis calc'd for C₁₃ H₁₂ Cl₃ F₂ N₃ O₂ : C 40.39, H 3.13, N 10.87.Found: C 40.92, H 3.28, N 10.96.

Step D1-(2,4-Dichloro-5-hydroxyphenyl)-3-chlorodifluoromethyl-4,5-dihydro-4-methyl-1,2,4-triazol-5(1H)-one

Hydrolysis of 2.6 g (0.0067 mole) of1-[2,4-dichloro-5-(1-methylethoxy)phenyl]-3-chlorodifluoromethyl-4,5-dihydro-4-methyl-1,2,4-triazol-5(1H)-onein 10 mL of concentrated sulfuric acid produced 2.17 g of1-(2,4-dichloro-5-hydroxyphenyl)-3-chlorodifluoromethyl-4,5-dihydro-4-methyl-1,2,4-triazol-5(1H)-oneas a solid (mp 146°-148° C.).

The nmr spectrum was consistent with the proposed structure.

Analysis calc'd for C₁₀ H₆ Cl₃ F₂ N₃ O₂ : C 34.86, H 1.76, N 12.20.Found: C 35.30, H 1.59, N 12.25.

HERBICIDAL ACTIVITY

The plant test species used in demonstrating the herbicidal activity ofcompounds of this invention include cotton (Gossypium hirsutum var.Stoneville), soybean (Glycine max var. Williams), field corn (Zea maysvar. Agway 595S), wheat (Triticum aestivium var. Prodax), rice (Oryzasativa), field bindweed (Convolvulus arvensis), morningglory (Ipomealacunosa or Ipomea hederacea, velvetleaf (Abutilon theophrasti),barnyardgrass (Echinochloa crus galli), green foxtail (Setaria viridis),and johnsongrass (Sorghum halepense), yellow nutsedge (Cyperusesculentus).

Seeds or tubers of the plant test species were planted in furrows insteam sterilized sandy loam soil contained in disposable fiber flats. Atopping soil of equal portions of sand and sandy loam soil was placeduniformly on top of each flat to a depth of approximately 0.5 cm.

The flats for the preemergence test were watered, then drenched with theappropriate amount of a solution of the test compound in a mixture ofacetone and water containing a small amount (up to 0.5% v/v) of sorbitanmonolaurate emulsifier/solubilizer. The concentration of the testcompound in solution was varied to give a range of application rates,generally 8.0 kg/ha and submultiples thereof. The flats were placed in agreenhouse and watered regularly at the soil surface for 21 days atwhich time phytotoxicity data were recorded.

The flats for the postemergence test were placed in a greenhouse andwatered for 8-10 days, then the foilage of the emerged test plants wassprayed with a solution of the test compound in acetone-water containingup to 0.5% sorbitan monolaurate. After spraying, the foilage was keptdry for 24 hours, then watered regularly for 21 days, and phytotoxicitydata recorded.

Phytotoxicity data were taken either as percent kill or percent control.Percent control was determined by a method similar to the 0 to 100rating system disclosed in "Research Methods in Weed Science," 2nd ed.,B. Truelove, Ed.; Southern Weed Science Society; Auburn University,Auburn, Ala., 1977. The present rating system ia as follows:

    ______________________________________                                        Herbicide Rating System                                                       Rating Description                                                            Percent                                                                              of Main   Crop          Weed                                           Control                                                                              Categories                                                                              Description   Description                                    ______________________________________                                         0     No effect No crop       No weed                                                         reduction     control                                                         or injury                                                    10               Slight dis-   Very poor weed                                                  coloration    control                                                         or stunting                                                  20     Slight    Some dis-     Poor weed                                             effect    coloration,   control                                                         stunting or                                                                   stand loss                                                   30               Crop injury   Poor to defi-                                                   more pronounced                                                                             cient weed                                                      but not lasting                                                                             control                                        40               Moderate injury,                                                                            Deficient weed                                                  crop usually  control                                                         recovers                                                     50     Moderate  Crop injury   Deficient to                                          effect    more lasting, moderate weed                                                   recovery      control                                        60               Lasting crop  Moderate weed                                                   injury no     control                                                         recovery                                                     70               Heavy injury and                                                                            Control some-                                                   stand loss    what less than                                                                satisfactory                                   80     Severe    Crop nearly des-                                                                            Satisfactory                                                    troyed a few  to good weed                                                    survivors     control                                        90               Only occasional                                                                             Very good to                                                    live plants left                                                                            excellent                                                                     control                                        100    Complete  Complete crop Complete weed                                         effect    destruction   destruction                                    ______________________________________                                    

Herbicidal data at selected application rates are given for variouscompounds of the invention in the tables below. The test compounds areidentified in the tables of herbicidal data below by numbers whichcorrespond to those used above.

In the Tables of herbicidal data below:

"kg/ha" is kilograms per hectare,

"% K" is percent kill, and

"% C" is percent control.

For herbicidal application, the active compounds as above defined areformulated into herbicidal compositions by admixture in herbicidallyeffective amounts with adjuvants and carriers normally employed in theart for facilitating the dispersion of active ingredients for theparticular utility desired, recognizing the fact that the formulationand mode of application of a toxicant may affect the activity of thematerial in a given application. Thus, for agricultural use the presentherbicidal compounds may be formulated as granules of relatively largeparticle size, water-soluble or water-dispersible granules, as powderydusts, as wettable powders, as emulsifiable concentrates, as solutionsor as any of several other known types of formulations, depending on thedesired mode of application.

For preemergence application these herbicidal compositions are usuallyapplied either as sprays, dusts, or granules to the areas in whichsuppression of vegetation is desired. For postemergence control ofestablished plant growth, sprays or dusts are most commonly used. Theseformulations may contain as little as 0.5% to as much as 95% or more byweight of active ingredient.

Dusts are free flowing admixtures of the active ingredient with finelydivided solids such as talc, natural clays, kieselguhr, flours such aswalnut shell and cottonseed flours, and other organic and inorganicsolids which act as dispersants and carriers for the toxicant; thesefinely divided solids have an average particle size of less than about50 microns. A typical dust formulation useful herein is one containing1.0 part of the herbicidal compound and 99.0 parts of talc.

Wettable powders, also useful formulations for both pre- andpostemergence herbicides, are in the form of finely divided particleswhich disperse readily in water or other dispersant. The wettable powderis ultimately applied to the soil either as a dry dust or as an emulsionin water or other liquid. Typical carriers for wettable powders includeFuller's earth, kaolin clays, silicas, and other highly absorbent,readily wet inorganic diluents. Wettable powders normally are preparedto contain about 5-80% of active ingredient, depending on the absorbencyof the carrier, and usually also contain a small amount of a wetting,dispersing or emulsifying agent to facilitate dispersion. For example, auseful wettable powder formulation contains 80.8 parts of the herbicidalcompound, 17.9 parts of Palmetto clay, and 1.0 part of sodiumlignosulfonate and 0.3 part of sulfonated aliphatic polyester as wettingagents. Frequently, additional wetting agent and/or oil will be added tothe tank-mix for postemergence application to facilitate dispersion onthe foliage and absorption by the plant.

Other useful formulations for herbicidal applications are emulsifiableconcentrates. Emulsifiable concentrates are homogeneous liquid or pastecompositions dispersible in water or other dispersant, and may consistentirely of the herbicidal compound and a liquid or solid emulsifyingagent, or may also contain a liquid carrier, such as xylene, heavyaromatic naphthas, isophorone, or other non-volatile organic solvent.For herbicidal application these concentrates are dispersed in water orother liquid carrier, and normally applied as a spray to the area to betreated. The percentage by weight of the essential active ingredient mayvary according to the manner in which the composition is to be applied,but in general comprises 0.5 to 95% of active ingredient by weight ofthe herbicidal composition.

Typical wetting, dispersing or emulsifying agents used in agriculturalformulations include, for example, the alkyl and alkylaryl sulfonatesand sulfates and their sodium salts; polyhydric alcohols; and othertypes of surface active agents, many of which are available in commerce.The surface active agent, when used, normally comprises 1% to 15% byweight of the herbicidal composition.

Other useful formulations for herbicidal applications include simplesolutions of the active ingredient in a dispersant in which it iscompletely soluble at the desired concentration, such as acetone,alkylated naphthalenes, xylene or other organic solvents. Granularformulations, wherein the toxicant is carried on relatively coarseparticles, are of particular utility for aerial distribution or forpenetration of cover crop canopy. Pressurized sprays, typically aerosolswherein the active ingredient is dispersed in finely divided form as aresult of vaporization of a low boiling dispersant solvent carrier, suchas the Freons, may also be used. Water-soluble or water-dispersiblegranules are also useful formulations for herbicidal application of thepresent compounds. Such granular formulations are free-flowing,non-dusty, and readily water-soluble or water-miscible. The soluble ordispersible granular formulations described in U.S. Pat. No. 3,920,442,incorporated herein by reference, are useful herein with the presentherbicidal compounds.

The active herbicidal compounds of this invention may be formulatedand/or applied with insecticides, fungicides, nematicides, plant growthregulators, fertilizers, or other agricultural chemicals and may be usedas effective soil sterilants as well as selective herbicides inagriculture. In applying an active compound of this invention, whetherformulated alone or with other agricultural chemicals, an effectiveamount and concentration of the active compound is of course employed;the amount may be as low as, for example, 7 g/ha or lower.

The active herbicidal compounds of this invention may be used incombination with other herbicides, e.g. they may be mixed with, say, anequal or larger amount of a known herbicide such as chloroacetanilideherbicides such as2-chloro-N-(2,6-diethylphenyl)-N-(methoxymethyl)acetamide (alachlor),2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)-acetamide(metolachlor), and N-chloroacetyl-N-(2,6-diethylphenyl)glycine(diethatyl-ethyl); benzothiadiazinone herbicides such as3-(1-methylethyl)-(1H)-2,1,3-benzothiadiazin-4-(3H)-one-2,2-dioxide(bentazon); triazine herbicides such as6-chloro-N-ethyl-N-(1-methylethyl)-1,3,5-triazine-2,4-diamine(atrazine), and2-[4-chloro-6-(ethylamino)-1,3,5-triazin-2-yl]-amino-2-methylpropanenitrile(cyanazine); dinitrolaniline herbicides such as2,6-dinitro-N,N-dipropyl-4-(trifluoromethyl)benzeneamine (trifluralin);and aryl urea herbicides such asN'-(3,4-dichlorophenyl)-N,N-dimethylurea (diuron) andN,N-dimethyl-N'-[3-(trifluoromethyl)phenyl]urea (fluometuron).

It is apparent that various modifications may be made in the formulationand application of the compounds of this invention, without departingfrom the inventive concepts herein, as defined in the following claims.

                  TABLE 1                                                         ______________________________________                                        Percent Control                                                                          Pre-Emergent    Post-Emergent                                      PLANT        A       B         A     B                                        ______________________________________                                        Cotton       50      0         90    40                                       Soybean      10      0          0    10                                       Corn          0      0          0    0                                        Rice         50      20        40    0                                        Wheat        30      0         40    20                                       Field Bindweed                                                                             60      0         40    0                                        Morningglory 20      0         60    10                                       Velvetleaf   100     0         100   0                                        Barnyardgrass                                                                              70      0         90    0                                        Green foxtail                                                                              100     70        90    0                                        Johnsongrass 40      0         10    0                                        Yellow nutsedge                                                                            30      0         10    0                                        ______________________________________                                    

                                      TABLE 2                                     __________________________________________________________________________     ##STR17##                                                                    Cmpd.                                                                         No. X  Y            R.sup.1  R.sup.2                                                                           R.sup.3                                                                              R.sup.4                               __________________________________________________________________________     1  Cl Cl           CH.sub.3 CHF.sub.2                                                                         CH.sub.2                                                                             CH.sub.3                               2  Cl Cl           CH.sub.3 CHF.sub.2                                                                         CH(CH.sub.3)                                                                         CH.sub.3                               3  F  Cl           CH.sub.3 CHF.sub.2                                                                         CH(CH.sub.3)                                                                         CH.sub.3                               4  Cl CH.sub.3     CH.sub.3 CHF.sub.2                                                                         CH(CH.sub.3)                                                                         CH.sub.3                               5  Cl Cl           CH.sub.3 CHF.sub.2                                                                         CH(CH.sub.3)                                                                         C.sub.2 H.sub.5                        6  F  Cl           CH.sub.3 CHF.sub.2                                                                         CH(CH.sub.3)                                                                         C.sub.2 H.sub.5                        7  Cl CH.sub.3     CH.sub.3 CHF.sub.2                                                                         CH(CH.sub.3)                                                                         C.sub.2 H.sub.5                        8  Br Br           CH.sub.3 CHF.sub.2                                                                         CH(CH.sub.3)                                                                           -n-C.sub.2 H.sub.5                   9  Cl Cl           CH.sub.3 CHF.sub.2                                                                         CH(CH.sub.3)                                                                         C.sub.3 H.sub.7                       10  Cl Cl           CH.sub.3 CHF.sub.2                                                                         CH(CH.sub.3)                                                                         CH(CH.sub.3).sub.2                    11  Cl Cl           CH.sub.3 CHF.sub.2                                                                         CH(CH.sub.3)                                                                         C.sub.4 H.sub.9                       12  Cl Cl           CH.sub.3 CHF.sub.2                                                                         CH(CH.sub.3)                                                                         CH(CH.sub.3)C.sub.2 H.sub.5           13  Cl Cl           CH.sub.3 CH.sub.2 F                                                                        CH(CH.sub.3)                                                                         C.sub.2 H.sub.5                       14  F  Cl           CH.sub.3 CHF.sub.2                                                                         CH.sub.2                                                                             CH.sub.3                              15  F  Cl           CH.sub.3 CHF.sub.2                                                                         CH(CH.sub.3)                                                                          -n-C.sub.3 H.sub.7                   16  F  Cl           CH.sub.3 CHF.sub.2                                                                         CH(CH.sub.3)                                                                         CH(CH.sub.3).sub.2                    17  Cl Cl           CH.sub.3 CHF.sub.2                                                                         CH.sub.2                                                                             C.sub.2 H.sub.5                       18  Cl Cl           CH.sub.3 CHF.sub.2                                                                         CH.sub.2 CH.sub.2 CH.sub.2                                                           C.sub.2 H.sub.5                       19  F  Cl           CH.sub.3 CHF.sub.2                                                                         CH(CH.sub.3)                                                                         C(CH.sub.3).sub.3                     20  F  Cl           CH.sub.3 CHF.sub.2                                                                         C(CH.sub.3).sub.2                                                                    C.sub.2 H.sub.5                       21  Cl Cl           CH.sub.3 CHF.sub.2                                                                         CH.sub.2                                                                             C(CH.sub.3).sub.3                     22  F  Cl           CH.sub.3 CHF.sub.2                                                                         CH.sub.2                                                                             C(CH.sub.3).sub.3                     23  Cl CH.sub.2 F   CH.sub.3 CHF.sub.2                                                                         CH(CH.sub.3)                                                                         C.sub.2 H.sub.5                       24  F  Cl           CH.sub.3 CHF.sub.2                                                                         CH(CH.sub.3)                                                                         CH.sub.2 CH(CH.sub.3).sub.2           25  F  F            CH.sub.3 CHF.sub.2                                                                         CH(CH.sub.3)                                                                         C.sub.2 H.sub.5                       26  Cl F            CH.sub.3 CHF.sub.2                                                                         CH(CH.sub.3)                                                                         C.sub.2 H.sub.5                       27  Cl CH.sub.2 F   CH.sub.3 CHF.sub.2                                                                         CH(CH.sub.3)                                                                         C.sub.2 H.sub.5                       28  F  CH.sub.2 F   CH.sub.3 CHF.sub.2                                                                         CH(CH.sub.3)                                                                         C.sub.2 H.sub.5                       29  F  CH.sub.3     CH.sub.3 CHF.sub.2                                                                         CH(CH.sub.3)                                                                         C.sub.2 H.sub.5                       30  Cl CH.sub.2 OCH.sub.3                                                                         CH.sub.3 CHF.sub.2                                                                         CH(CH.sub.3)                                                                         CH.sub.3                              31  Cl CH.sub.2 SO.sub.2 CH.sub.3                                                                 CH.sub.3 CHF.sub.2                                                                         CH.sub.2                                                                             C.sub.2 H.sub.5                       32  F  CH.sub.2 SCH.sub.2 CHCH.sub.2                                                              CH.sub.3 CHF.sub.2                                                                         CH(CH.sub.3)                                                                         C.sub.2 H.sub.5                       33  F  CH.sub.2 OCH.sub.2 CHCH                                                                    CH.sub.3 CHF.sub.2                                                                         CH(CH.sub.3)                                                                         C.sub.2 H.sub.5                       34  F  Cl           Cl       CHF.sub.2                                                                         CH(CH.sub.3)                                                                         C.sub.2 H.sub.5                       35  F  Cl           C.sub.2 H.sub.5                                                                        CHF.sub.2                                                                         CH(CH.sub.3)                                                                         C.sub.2 H.sub.5                       36  F  Cl           CH.sub.2 CN                                                                            CHF.sub.2                                                                         CH(CH.sub.3)                                                                         C.sub.2 H.sub.5                       37  F  Cl           CH.sub.2 SCH.sub.3                                                                     CHF.sub.2                                                                         CH(CH.sub.3)                                                                         C.sub.2 H.sub.5                       38  F  Cl           CHF.sub.2                                                                              CHF.sub.2                                                                         CH(CH.sub.3)                                                                         CH.sub.3                              39  F  Cl           CF.sub.3 CHF.sub.2                                                                         CH(CH.sub.3)                                                                         CH(CH.sub.3).sub.2                    40  F  Cl                                                                                          ##STR18##                                                                             CHF.sub.2                                                                         CH.sub.2                                                                             C.sub.2 H.sub.5                       41  F  Cl           SCH.sub.3                                                                              CHF.sub.2                                                                         CH(CH.sub.3)                                                                         CH.sub.3                              42  F  Cl           SO.sub.2 CH.sub.3                                                                      CHF.sub.2                                                                         CH(CH.sub.3)                                                                         CH.sub.3                              43  F  Cl           CH.sub.2 SO.sub.2 CH.sub.3                                                             CHF.sub.2                                                                         CH(CH.sub.3)                                                                         C.sub.2 H.sub.5                       44  F  Cl           CH.sub.3 CH.sub.2 F                                                                        CH.sub.2                                                                             C.sub.2 H.sub.5                       45  F  CH.sub.2 SOCH.sub.2 CH.sub.3                                                               CH.sub.3 CHF.sub.2                                                                         CH(CH.sub.3)                                                                         CH.sub.3                              46  F  CH.sub.2 SCH.sub.2 CHCH                                                                    CH.sub.3 CHF.sub.2                                                                         CH.sub.2                                                                             C.sub.2 H.sub.5                       47  F  CH.sub.2 OCH.sub.2 CHCHCH.sub.3                                                            CH.sub.3 CHF.sub.2                                                                         CH(CH.sub.3)                                                                         CH.sub.3                              48  F  CH.sub.2 SCH.sub.2 C(CH.sub.3)CH.sub.2                                                     CH.sub.3 CHF.sub.2                                                                         CH.sub.2                                                                             CH.sub.3                              49  CF.sub.3                                                                         Cl           CH.sub.3 CHF.sub.2                                                                         CH(CH.sub.3)                                                                         C.sub.2 H.sub.5                       50  F                                                                                 ##STR19##   CH.sub.3 CHF.sub.2                                                                         CH(CH.sub.3)                                                                         C.sub.2 H.sub.5                       51  Cl Cl           CH.sub.3 CHF.sub.2                                                                         CHF    C.sub.2 H.sub.5                       52  F  Cl           CHF.sub.2                                                                              CH.sub.3                                                                          CH(CH.sub.3)                                                                         C(CH.sub.3).sub.3                     53  F  Cl           CHF.sub.2                                                                              CH.sub.3                                                                          CH(CH.sub.3)                                                                         CH.sub.3                              54  F  Cl           CHF.sub.2                                                                              CH.sub.3                                                                          CH(CH.sub.3)                                                                          -n-C.sub.3 H.sub.7                   55  F  Br           CHF.sub.2                                                                              CH.sub.3                                                                          CH(CH.sub.3)                                                                         C.sub.2 H.sub.5                       56  F  Br           CH.sub.3 CHF.sub.2                                                                         CH(CH.sub.3)                                                                         C.sub.2 H.sub.5                       57  Br Br           CHF.sub.2                                                                              CH.sub.3                                                                          CH(CH.sub.3)                                                                         C.sub.2 H.sub.5                       58  F  Cl           CHF.sub.2                                                                              CH.sub.3                                                                          CH(CH.sub.3)                                                                         CH(CH.sub.3).sub.2                    59  F  Cl           CHF.sub.2                                                                              CH.sub.3                                                                          CH(CH.sub.3)                                                                         CH.sub.2 CH(CH.sub.3).sub.2           60  Cl Cl           CHF.sub.2                                                                              CH.sub.3                                                                          CH(CH.sub.3)                                                                         C.sub.2 H.sub.5                       61  F  Br           CH.sub.3 CHF.sub.2                                                                         CH(CH.sub.3)                                                                          -n-C.sub.3 H.sub.7                   62  F  CF.sub.3     CH.sub.3 CHF.sub.2                                                                         CH(CH.sub.3)                                                                         C.sub.2 H.sub.5                       63  F  Br           CH.sub.3 CHF.sub.2                                                                         CH(CH.sub.3)                                                                         C(CH.sub.3).sub.3                     64  Cl Br           CH.sub.3 CHF.sub.2                                                                         CH(CH.sub.3)                                                                         C.sub.2 H.sub.5                       65  Br Cl           CH.sub.3 CHF.sub.2                                                                         CH(CH.sub.3)                                                                         C.sub.2 H.sub.5                       __________________________________________________________________________

Other representative compounds are those which are identical withcompounds 1-54, 57-60, 62, and 64-65 respectively, except that X is Fand Y is Br. Still other representative compounds are those which areidentical with compounds 1-61, and 63-65 respectively, except that X isF and Y is CF₃.

                                      TABLE 3                                     __________________________________________________________________________     ##STR20##                                                                    Cmpd.                                                                         No. X Y            R.sup.1                                                                             R.sup.2                                                                           R.sup.3                                                                            R.sup.4                                     __________________________________________________________________________    A1  Cl                                                                              Cl           CH.sub.3                                                                            CHF.sub.2                                                                         CH(CH.sub.3)                                                                       H                                           A2  F Cl           CH.sub.3                                                                            CHF.sub.2                                                                         CH(CH.sub.3)                                                                       H                                           A3  Cl                                                                              CH.sub.3     CH.sub.3                                                                            CHF.sub.2                                                                         CH(CH.sub.3)                                                                       H                                           A4  F Cl           CH.sub.3                                                                            CHF.sub.2                                                                         CH(CH.sub.3)                                                                       Na                                          A5  F Cl           CH.sub.3                                                                            CHF.sub.2                                                                         CH.sub.2                                                                           H                                           A6  F Cl           CH.sub.3                                                                            CHF.sub.2                                                                         CH(CH.sub.3)                                                                       NH.sub.3 CH(CH.sub.3).sub.2                 A7  F CH.sub.3     CH.sub.3                                                                            CHF.sub.2                                                                         CH(CH.sub.3)                                                                       H                                           A8  F CH.sub.3     CH.sub.3                                                                            CHF.sub.2                                                                         CH(CH.sub.3)                                                                       K                                           A9  Cl                                                                              CH.sub.2 F   CH.sub.3                                                                            CHF.sub.2                                                                         CH(CH.sub.3)                                                                       H                                           A10 Cl                                                                              CH.sub. 2 F  CH.sub.3                                                                            CHF.sub.2                                                                         CH(CH.sub.3)                                                                       NH.sub.4                                    A11 F Cl           CHF.sub.2                                                                           CHF.sub.2                                                                         CH(CH.sub.3)                                                                       H                                           A12 Br                                                                              Cl           CH.sub.2 CN                                                                         CHF.sub.2                                                                         CH(CH.sub.3)                                                                       H                                           A13 F Cl           CH.sub.2 SCH.sub.3                                                                  CHF.sub.2                                                                         CH.sub.2                                                                           H                                           A14 F Cl           CF.sub.3                                                                            CHF.sub.2                                                                         CH(CH.sub.3)                                                                       H                                           A15 F CH.sub.2 OCH.sub.3                                                                         CH.sub.3                                                                            CHF.sub.2                                                                         CH(CH.sub.3)                                                                       H                                           A16 F CH.sub.3     CH.sub.3                                                                            CHF.sub.2                                                                         CH(CH.sub.3)                                                                       H                                           A17 F CH.sub.3     CH.sub.3                                                                            CHF.sub.2                                                                         CH(CH.sub.3)                                                                       Na                                          A18 F CH.sub.2 SCH.sub.2 CHCH.sub.2                                                              CH.sub.3                                                                            CHF.sub.2                                                                         CH(CH.sub.3)                                                                       H                                           A19 F CH.sub.2 SO.sub.2 CH.sub.3                                                                 CH.sub.3                                                                            CHF.sub.2                                                                         CH.sub.2                                                                           HN(CH.sub.3).sub.3                          A20 F                                                                                ##STR21##   CH.sub.3                                                                            CHF.sub.2                                                                         CH(CH.sub.3)                                                                       H                                           A21 F Cl           CHF.sub.2                                                                           CH.sub.3                                                                          CH(CH.sub.3)                                                                       H                                           A22 F Br           CHF.sub.2                                                                           CH.sub.3                                                                          CH(CH.sub.3)                                                                       H                                           A23 F Br           CH.sub.3                                                                            CHF.sub.2                                                                         CH(CH.sub.3)                                                                       H                                           A24 Br                                                                              Br           CH.sub.3                                                                            CHF.sub.2                                                                         CH(CH.sub.3)                                                                       H                                           A25 Br                                                                              Br           CHF.sub.2                                                                           CH.sub.3                                                                          CH(CH.sub.3)                                                                       H                                           A26 F Cl           CHF.sub.2                                                                           CH.sub.3                                                                          CH(CH.sub.3)                                                                       Na                                          A27 Cl                                                                              Cl           CHF.sub.2                                                                           CH.sub.3                                                                          CH(CH.sub.3)                                                                       H                                           A28 Cl                                                                              Br           CH.sub.3                                                                            CHF.sub.2                                                                         CH(CH.sub.3)                                                                       H                                           A29 Br                                                                              Cl           CH.sub.3                                                                            CHF.sub.2                                                                         CH(CH.sub.3)                                                                       H                                           __________________________________________________________________________

Other representative compounds are those which are identical withcompounds A1-A21, and A24-A29 respectively, except that X is F and Y isBr. Still other representative compounds are those which are identicalwith compounds A1-A29 respectively, except that X is F and Y is CF₃.

                                      TABLE 4                                     __________________________________________________________________________     ##STR22##                                                                    Cmpd. No.                                                                           X Y         R.sup.1                                                                            R.sup.2  R.sup.3                                                                            ZR.sup.4                                 __________________________________________________________________________    B1    Cl                                                                              Cl        CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                       OCH.sub.2 CH(NO.sub.2)CH.sub.3           B2    Cl                                                                              Cl        CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                       OCH.sub.2 CHCH.sub.2                     B3    Cl                                                                              Cl        CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                       OCH.sub.2 CCH                            B4    F Cl        CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                       OCH.sub.2 CCH                            B5    Cl                                                                              Cl        CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                       OCH.sub.2 CH.sub.2 OCH.sub.3             B6    F Cl        CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                       OCH(CH.sub.3)C CH                        B7    F Cl        CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                       OC(CH.sub.3).sub.2 CCH                   B8    F Cl        CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                        ##STR23##                               B9    F Cl        CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                       OCH.sub.2 CO.sub.2 CH.sub.3              B10   F Cl        CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                       OC(CH.sub.3).sub.2 CF.sub.2 CHF.sub.2                                         1                                        B11   F Cl        CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                       OCH.sub.2 CN                             B12   F Cl        CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                        ##STR24##                               B13   F Cl        CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                       OCH.sub.2 CH.sub.2 N(CH.sub.3).sub.2                                          5                                        B14   F Cl        CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                        ##STR25##                               B15   F Cl        CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                        ##STR26##                               B16   F Cl        CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                        ##STR27##                               B17   F Cl        CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                       SC.sub.2 H.sub.5                         B18   F Cl        CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                       SCH.sub.2 CO.sub.2 C.sub.2 H.sub.5       B19   Cl                                                                              Cl        CH.sub.3                                                                           CHF.sub.2                                                                              CHF  SC.sub.2 H.sub.5                         B20   F Cl        CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                       OCH.sub.2 CH.sub.2 N(CH.sub.3).sub.3                                          Cl                                       B21   F Cl        CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                       OCH.sub.2 CON(C.sub.2 H.sub.5).sub.2     B22   F Cl        CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                       OCH.sub.2 OCH.sub.3                      B23   F Cl        CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                       OCH.sub.2 SCH.sub.3                      B24   F Cl        CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                       OCH.sub.2 S(O)CH.sub.3                   B25   F Cl        CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                       OCH.sub.2 SO.sub.2 CH.sub.3              B26   F Cl        CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                        ##STR28##                               B27   F Cl        CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                        ##STR29##                               B28   F Cl        CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                        ##STR30##                               B29   F Cl        CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                        ##STR31##                               B30   F Cl        CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                       OCH.sub.2 CF.sub.3                       B31   F Cl        CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                       OC(CH.sub.3).sub.2 CN                    B32   F Cl        CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                        ##STR32##                               B33   F Cl        CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                       SCH(CH.sub.3).sub.2                      B34   F Cl        CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                        ##STR33##                               B35   F Cl        CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                        ##STR34##                               B36   F Cl        CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                       SCH.sub.2 CHCH.sub.2                     B37   F CH.sub.3  CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                       SC.sub.2 H.sub.5                         B38   F CH.sub.3  CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                       OCH.sub.2 SCH.sub.3                      B39   F CH.sub.3  CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                       OCH.sub.2 S(O)CH.sub.3                   B40   F CH.sub.3  CH.sub. 3                                                                          CHF.sub.2                                                                              CH(CH.sub.3)                                                                       OCH.sub.2 SO.sub.2 CH.sub.3              B41   F CH.sub.3  CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                       OCH.sub.2 CN                             B42   F CH.sub.2 F                                                                              CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                        ##STR35##                               B43   F CH.sub.3  CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                        ##STR36##                               B44   Cl                                                                              Cl        CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                        ##STR37##                               B45   Cl                                                                              Cl        CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                       OCH.sub.2 SCH.sub.3                      B46   Cl                                                                              Cl        CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                       SC.sub.2 H.sub.5                         B47   Cl                                                                              Cl        CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                       OCH.sub.2 CONH.sub.2                     B48   Cl                                                                              Cl        CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                        ##STR38##                               B49   Cl                                                                              Cl        CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                        ##STR39##                               B50   F Cl        CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                        ##STR40##                               B51   F Cl        CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                        ##STR41##                               B52   F Cl        CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                        ##STR42##                               B53   F CH.sub.2 OCH.sub.3                                                                      CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                       OCH.sub.2 OCH.sub.3                      B54   F CH.sub.2 SCH.sub.2 CHCH.sub.2                                                           CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                        ##STR43##                               B55   F Cl        CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                        ##STR44##                               B56   F Cl        CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                        ##STR45##                               B57   F Cl        CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                       OCH(OCOCH.sub.3)CH.sub.3                 B58   F Cl        CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                        ##STR46##                               B59   Cl                                                                              Cl        CH.sub.3                                                                           CH.sub.2 F                                                                             CH.sub.2                                                                           OCH.sub.2 C(Cl)CHCl                      B60   Cl                                                                              Cl        CH.sub.3                                                                           CHF.sub.2                                                                              CH.sub.2                                                                            ##STR47##                               B61   F Cl        CH.sub.3                                                                           CHF.sub.2                                                                              CH.sub.2                                                                            ##STR48##                               B62   F Cl        CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                        ##STR49##                               B63   F Cl        CHF.sub.2                                                                          CH.sub.3 CH(CH.sub.3)                                                                       OCH.sub.2 SCH.sub.3                      B64   F Cl        CHF.sub.2                                                                          CH.sub.3 CH(CH.sub.3)                                                                       OC(CH.sub.3).sub.2 CCH                   B65   F Cl        CHF.sub.2                                                                          CH.sub.3 CH(CH.sub.3)                                                                       SCH(CH.sub.3).sub.2                      B66   F Cl        CF.sub.3                                                                           CH.sub.3 CH.sub.2                                                                           OCH.sub.2 CN                             B67   F Cl        CF.sub.2 Cl                                                                        CH.sub.3 CH(CH.sub.3)                                                                        ##STR50##                               B68   F CH.sub.3  CHF.sub.2                                                                          CH.sub.2 CN                                                                            CH.sub.2                                                                           OCH.sub.2 OCH.sub.3                      B69   F CH.sub.3  CHF.sub.2                                                                          CH.sub.2 SCN                                                                           CH(CH.sub.3)                                                                       OCH.sub.2 CH.sub.2 N(CH.sub.3).sub.2     B70   F Cl        CF.sub.3                                                                           CH.sub.2 CHCH.sub.2                                                                    CH.sub.2                                                                            ##STR51##                               B71   F Cl        CHF.sub.2                                                                          CH.sub.2 OCH.sub.3                                                                     CH.sub.2                                                                           OCH.sub.2 OCH.sub.3                      B72   F Cl        CHF.sub.2                                                                          CH.sub.2 SO.sub.2 CH.sub.2 CH.sub.3                                                    CH(CH.sub.3)                                                                       OCH.sub.2 CHCH.sub.2                     B73   F Cl        CHF.sub.2                                                                          CH.sub.2 CH.sub.3                                                                      CH(CH.sub.3)                                                                       OCH.sub.2 CCH                            B74   F Cl        CF.sub.2 CF.sub.3                                                                  CH.sub.3 CH(CH.sub.3)                                                                       OCH.sub.2 OCH.sub.3                      B75   Cl                                                                              Cl        CF.sub.2 CF.sub.3                                                                  CH.sub.2 CHCH.sub.2                                                                    CH(CH.sub.3)                                                                       OCH.sub.2 CN                             B76   F Cl        CHF.sub.2                                                                          CHF.sub.2                                                                              CH(CH.sub.3)                                                                       OCH.sub.2 SCH.sub.3                      B77   F CH.sub.2 SCH.sub.3                                                                      CHF.sub.2                                                                          CH.sub.3 CH(CH.sub.3)                                                                       OCH.sub.2 CHCH.sub.2                     B78   F Cl        CHF.sub.2                                                                          CH.sub.3 CH(CH.sub.3)                                                                       OCH(CH.sub.3)CONH.sub.2                  B79   F Cl        Cl   CHF.sub.2                                                                              CH(CH.sub.3)                                                                       OCH.sub.2 CN                             B80   F Cl        SCH.sub.3                                                                          CHF.sub.2                                                                              CH(CH.sub.3)                                                                       OCH.sub.2 SCH.sub.3                      B81   F Cl        CH.sub.2 CN                                                                        CHF.sub.2                                                                              CH.sub.2                                                                           OCH.sub.2 CHCH.sub.2                     B82   F                                                                                ##STR52##                                                                              CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                       OCH.sub.2 SCH.sub.3                      B83   F Cl        CHF.sub.2                                                                          CH.sub.3 CH(CH.sub.3)                                                                       SCH.sub.2 CO.sub.2 CH.sub.3              B84   F Cl        CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                        ##STR53##                               B85   F Cl        CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                        ##STR54##                               B86   F Cl        CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                        ##STR55##                               B87   F Cl        CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                        ##STR56##                               B88   F Cl        CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                        ##STR57##                               B89   F Br        CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                        ##STR58##                               B90   Br                                                                              Br        CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                        ##STR59##                               B91   F Br        CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                       OC(CH.sub.3).sub.2 CCH                   B92   Cl                                                                              Cl        CHF.sub.2                                                                          CH.sub.3 CH(CH.sub.3)                                                                        ##STR60##                               B93   F Cl        CHF.sub.2                                                                          CH.sub.3 CH(CH.sub.3)                                                                        ##STR61##                               B94   F Cl        CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                        ##STR62##                               B95   F Cl        CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                        ##STR63##                               B96   F Cl        CH.sub.3                                                                           CHF.sub.2                                                                              CH(CH.sub.3)                                                                        ##STR64##                               __________________________________________________________________________

Other representative compounds are those which are identical withcompounds B1-B88, B-90, and B92-B96 respectively, except that X is F andY is Br. Still other representative compounds are those which areidentical with compounds B1-B96 respectively, except that X is F and Yis CF₃.

                                      TABLE 5                                     __________________________________________________________________________     ##STR65##                                                                    Cmpd.                                                                         No. X   Y         R.sup.1                                                                             R.sup.2 R.sup.3                                                                             R.sup.6            R.sup.7              __________________________________________________________________________    C1  Cl  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH.sub.2                                                                            H                  H                    C2  F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        CH.sub.3           H                    C3  Cl  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        SO.sub.2 CH.sub.3  H                    C4  Cl  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        SO.sub.2 CF.sub.3  H                    C5  Cl  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        H                  H                    C6  Cl  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        CH.sub.3           H                    C7  F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH.sub.2                                                                            H                  H                    C8  F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH.sub.2                                                                            C.sub.2 H.sub.5    C.sub.2 H.sub.5      C9  F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        CH(CH.sub.3)C.sub.2 H.sub.5                                                                      H                    C10 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR66##         H                    C11 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        OCH.sub.3          CH.sub.3             C12 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        CH.sub.2 CCH       H                    C13 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR67##         H                    C14 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        CH.sub.3           CH.sub.3             C15 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        C.sub.2 H.sub.5    C.sub.2 H.sub.5      C16 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        C.sub.2 H.sub.5    H                    C17 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        CH.sub.2 CO.sub.2 CH.sub.3                                                                       H                    C18 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        SO.sub.2 CH.sub.3  H                    C19 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        SO.sub.2 CH.sub. 3 Na                   C20 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR68##         Na                   C21 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        C(CH.sub.3).sub.2 CCH                                                                            H                    C22 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        C(CH.sub.3).sub.2 CN                                                                             H                    C23 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR69##         CH.sub.3             C24 Cl  Cl        CHF.sub.2                                                                           CH.sub.3                                                                              CH.sub.2                                                                            H                  H                    C25 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR70##         H                    C26 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        H                  H                    C27 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        SO.sub.2 CF.sub.3  H                    C28 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        SO.sub.2 CF.sub.3  Na                   C29 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR71##         H                    C30 F   Cl        CH.sub. 3                                                                           CHF.sub.2                                                                             CH(CH.sub.3)                                                                        SO.sub.2 CH.sub.3  CH.sub.3             C31 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR72##         CH.sub.3             C32 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR73##         H                    C33 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH.sub.2                                                                            SO.sub.2 CH.sub.3  H                    C34 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH.sub.2                                                                             ##STR74##         H                    C35 F   CH.sub.3  CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        NHCH.sub.3         H                    C36 F   CH.sub.3  CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        SO.sub.2 CH.sub.3  H                    C37 F   CH.sub.3  CH.sub.3                                                                            CHF.sub.2                                                                             CH.sub.2                                                                            SO.sub.2 CH.sub.3  H                    C38 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2     C39 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        CH.sub.2 CH.sub.2 OCH.sub.2                                                   CH.sub.2                                C40 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         SO.sub.2 N(CH.sub.3).sub.2                                                                      H                    C41 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        SO.sub.2 NHCH(CH.sub.3).sub.2                                                                    H                    C42 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR75##         H                    C43 F   Cl        CHF.sub.2                                                                           CH.sub.3                                                                              CH(CH.sub.3)                                                                         ##STR76##         H                    C44 F   Cl        CF.sub.2 Cl                                                                         CH.sub.3                                                                              CH(CH.sub.3)                                                                        H                  CH.sub.3             C45 F   CH.sub.3  CHF.sub.2                                                                           CH.sub.3                                                                              CH(CH.sub.3)                                                                        SO.sub.2 CH.sub.3  H                    C46 F   CH.sub.2 SCH.sub.3                                                                      CHF.sub.2                                                                           CH.sub.3                                                                              CH.sub.2                                                                            CH.sub.3           CH.sub.3             C47 F   Cl        CHF.sub.2                                                                           CH.sub.2 CN                                                                           CH(CH.sub.3)                                                                        H                  H                    C48 F   Cl        CHF.sub.2                                                                           CH.sub.2 SCN                                                                          CH(CH.sub.3)                                                                        H                  CH(CH.sub.3).sub.                                                             2                    C49 F   Cl        CF.sub.3                                                                            CH.sub.2 OCH.sub.3                                                                    CH.sub.2                                                                            CH.sub.2 CHCH.sub.2                                                                              H                    C50 F   Cl        CF.sub.3                                                                            CH.sub.2 CHCH.sub.2                                                                   CH(CH.sub.3)                                                                         ##STR77##         H                    C51 F   Cl        CHF.sub.2                                                                           CHF.sub.2                                                                             CH(CH.sub.3)                                                                        H                  H                    C52 Cl  Cl        CHF.sub.2                                                                           CH.sub.3                                                                              CH.sub.2                                                                             ##STR78##         H                    C53 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        CH.sub.2 CH.sub.2 OCH.sub.3                                                                      H                    C54 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR79##         H                    C55 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH.sub.2                                                                            SO.sub.2 CH.sub.2 CHCH.sub.2                                                                     H                    C56 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH.sub.2                                                                            SO.sub.2 CH.sub.2 CHCH.sub.2                                                                     Na                   C57 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2                                           CH.sub.2                                C58 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR80##         H                    C59 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR81##         H                    C60 Cl  Cl        CHF.sub.2                                                                           CH.sub. 3                                                                             CH(CH.sub.3)                                                                        SO.sub.2 N(CH.sub.3).sub.2                                                                       H                    C61 F   Cl        CHF.sub.2                                                                           CHF.sub.2                                                                             CH(CH.sub.3)                                                                        H                  H                    C62 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR82##                              C63 CF.sub.3                                                                          Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        H                  H                    C64 F   Cl        CH.sub.2 CN                                                                         CHF.sub.2                                                                             CH(CH.sub.3)                                                                        H                  H                    C65 F   Cl        CH.sub.2 SCH.sub.3                                                                  CHF.sub.2                                                                             CH.sub.2                                                                            CH.sub.3           H                    C66 F   Cl        SCH.sub.3                                                                           CHF.sub.2                                                                             CH(CH.sub.3)                                                                        CH.sub.3           CH.sub.3             C67 F   Cl        Cl    CHF.sub.2                                                                             CH(CH.sub.3)                                                                        H                  H                    C68 F                                                                                  ##STR83##                                                                              CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        H                  H                    C69 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH.sub.2                                                                             ##STR84##         H                    C70 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH.sub.2                                                                             ##STR85##         H                    C71 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR86##         Na                   C72 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR87##         H                    C73 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR88##         H                    C74 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR89##         H                    C75 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR90##         H                    C76 Cl  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR91##         H                    C77 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR92##         H                    C78 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR93##         H                    C79 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR94##         CH.sub.3             C80 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR95##         H                    C81 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR96##         H                    C82 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR97##         H                    C83 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR98##         Na                   C84 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR99##         CH.sub.3             C85 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR100##        H                    C86 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR101##                             C87 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR102##        H                    C88 F   Cl        CH.sub.3                                                                            CH.sub.3                                                                              CH(CH.sub.3)                                                                         ##STR103##        H                    C89 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR104##                             C90 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR105##        H                    C91 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR106##        Na                   C92 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR107##        Na                   C93 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR108##        H                    C94 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR109##        H                    C95 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR110##        H                    C96 F   Br        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2     C97 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR111##                             C98 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR112##        Na                   C99 F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR113##        H                    C100                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR114##        Na                   C101                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR115##        H                    C102                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR116##                             C103                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR117##                             C104                                                                              F   Cl        CH.sub.3                                                                            CHF.sub. 2                                                                            CH(CH.sub.3)                                                                         ##STR118##                             C105                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR119##        H                    C106                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR120##        Na                   C107                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR121##        H                    C108                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR122##                             C109                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR123##        H                    C110                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR124##        Na                   C111                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR125##        H                    C112                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH.sub.2                                                                             ##STR126##        H                    C113                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR127##        H                    C114                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR128##        Na                   C115                                                                              F   Br        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR129##        H                    C116                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH.sub.2                                                                             ##STR130##        H                    C117                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR131##        H                    C118                                                                              Cl  Cl        CClF.sub.2                                                                          CH.sub.3                                                                              CH(CH.sub.3)                                                                         ##STR132##        H                    C119                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH.sub.2                                                                             ##STR133##        H                    C120                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH.sub.2                                                                             ##STR134##        H                    C121                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH.sub.2                                                                             ##STR135##        Na                   C122                                                                              Cl  Cl        CHF.sub.2                                                                           CH.sub.3                                                                              CH(CH.sub.3)                                                                         ##STR136##        H                    C123                                                                              F   Br        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR137##        H                    C124                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR138##        H                    C125                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR139##        H                    C126                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR140##        H                    C127                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR141##        H                    C128                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR142##        H                    C129                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH.sub.2                                                                             ##STR143##        H                    C130                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH.sub.2                                                                             ##STR144##        Na                   C131                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR145##        H                    C132                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR146##        Na                   C133                                                                              F   Br        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR147##        H                    C134                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR148##        H                    C135                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR149##        H                    C136                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR150##        H                    C137                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR151##        H                    C138                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR152##        H                    C139                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR153##        Na                   C140                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR154##        H                    C141                                                                              F   Br        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR155##        H                    C142                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR156##        H                    C143                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR157##        H                    C144                                                                              F   Br        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR158##        H                    C145                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR159##        H                    C146                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR160##        H                    C147                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR161##        H                    C148                                                                              F   Br        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR162##        H                    C149                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR163##        H                    C150                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR164##        H                    C151                                                                              F   Br        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR165##        H                    C152                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR166##        H                    C153                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR167##        H                    C154                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR168##        H                    C155                                                                              Cl  Cl        CHF.sub.2                                                                           CH.sub.3                                                                              CH(CH.sub.3)                                                                         ##STR169##        H                    C156                                                                              Cl  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR170##        H                    C157                                                                              F   Br        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        SO.sub.2 CH.sub.3  H                    C158                                                                              F   Br        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        SO.sub.2 CF.sub.3  H                    C159                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        SO.sub.2 NH.sub.2  H                    C160                                                                              F   Br        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR171##        H                    C161                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR172##        H                    C162                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR173##        H                    C163                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR174##        H                    C164                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR175##        H                    C165                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR176##        H                    C166                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR177##        H                    C167                                                                              F   Br        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR178##        H                    C168                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR179##        H                    C169                                                                              F   Br        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR180##        H                    C170                                                                              F   Cl        CHF.sub.2                                                                           CH.sub.3                                                                              CH(CH.sub.3)                                                                         ##STR181##        H                    C171                                                                              F   Br        CHF.sub.2                                                                           CH.sub.3                                                                              CH(CH.sub.3)                                                                         ##STR182##        H                    C172                                                                              F   Br        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR183##        H                    C173                                                                              F   Cl        CHF.sub.2                                                                           CH.sub.3                                                                              CH(CH.sub.3)                                                                         ##STR184##        H                    C174                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR185##        H                    C175                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR186##        H                    C176                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR187##        H                    C177                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR188##        H                    C178                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR189##        H                    C179                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR190##        H                    C180                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR191##        H                    C181                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR192##        H                    C182                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR193##        H                    C183                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR194##        H                    C184                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR195##        H                    C185                                                                              F   Br        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        H                  H                    C186                                                                              F   Br        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        CH.sub.3           H                    C187                                                                              F   Br        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        CH.sub.3           CH.sub.3             C188                                                                              F   Br        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        C.sub.2 H.sub.5    H                    C189                                                                              F   Cl        CHF.sub.2                                                                           CH.sub.3                                                                              CH(CH.sub.3)                                                                         ##STR196##        H                    C190                                                                              F   Cl        CHF.sub.2                                                                           CH.sub.3                                                                              CH(CH.sub.3)                                                                        H                  H                    C191                                                                              F   Cl        CHF.sub.2                                                                           CH.sub.3                                                                              CH(CH.sub.3)                                                                        CH.sub.3           H                    C192                                                                              F   Cl        CHF.sub.2                                                                           CH.sub.3                                                                              CH(CH.sub.3)                                                                        CH.sub.3           CH.sub.3             C193                                                                              F   Br        CHF.sub.2                                                                           CH.sub.3                                                                              CH(CH.sub.3)                                                                        CH.sub.3           CH.sub.3             C194                                                                              F   Br        CHF.sub.2                                                                           CH.sub.3                                                                              CH(CH.sub.3)                                                                        H                  H                    C195                                                                              F   Br        CHF.sub.2                                                                           CH.sub.3                                                                              CH(CH.sub.3)                                                                        CH.sub.3           H                    C196                                                                              Br  Br        CHF.sub.2                                                                           CH.sub.3                                                                              CH(CH.sub.3)                                                                        CH.sub.3           CH.sub.3             C197                                                                              Br  Br        CHF.sub.2                                                                           CH.sub.3                                                                              CH(CH.sub.3)                                                                        H                  H                    C198                                                                              Br  Br        CHF.sub.2                                                                           CH.sub.3                                                                              CH(CH.sub.3)                                                                        CH.sub.3           H                    C199                                                                              Br  Br        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        CH.sub.3           H                    C200                                                                              Br  Br        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        H                  H                    C201                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR197##        H                    C202                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR198##        H                    C203                                                                              F   Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                         ##STR199##        H                    __________________________________________________________________________

Other representative compounds are those which are identical withcompounds C1-C95, C97-C114, C116-C122, C124-C132, C134-C140, C142-C143,C145-C147, C149-C150, C152-C156, C159, C161-C165, C168, C170, C173-C184,C186, C189-C192, and C196-C203 respectively, except that X is F and Y isBr. Still other representative compounds are those which are identicalwith Compounds C1-C203 respectively, except that X if F and Y is CF₃.

                                      TABLE 6                                     __________________________________________________________________________    Identifying Properties                                                        Cmpd.                                                                             Melting                          Elemental Analysis                       No. Point (°C.)                                                                  Empirical Formula          C  H   N                                 __________________________________________________________________________    1   111.5-113.5                                                                         C.sub.13 H.sub.11 Cl.sub.2 F.sub.2 N.sub.3 O.sub.4 4                          NMRδ(CDCl.sub.3): 2.45(s,3H), 3.80(s,3H),                               4.70(s,2H), 6.90(s,1H), 7.00(t,1H,J=                                          58 Hz), 7.50(s,1H).                                                 2   Oil   C.sub.14 H.sub.13 Cl.sub.2 F.sub.2 N.sub.3 O.sub.4                            NMRδ(CDCl.sub.3): 1.70(d,3H,J=7 Hz), 2.50                               (s,3H), 3.80(s,3H), 4.80(q,1H,J=7 Hz).                                        7.00(s,1H), 7.10(t,1H,J=58 Hz), 7.60                                          (s,1H).                                                             3   Oil   C.sub.14 H.sub.13 ClF.sub.3 N.sub.3 O.sub.4                                   NMRδ(CDCl.sub.3): 1.70(d,3H,J=7 Hz), 2.50                               (s,3H), 3.80(s,3H), 4.80(q,1H,J=7 Hz),                                        7.00(t,1H,J=58 Hz), 7.00-7.40(m,2H).                                4   Oil   C.sub.15 H.sub.16 ClF.sub.2 N.sub.3 O.sub.4                                   NMRδ(CDCl.sub.3): 1.65(d,3H,J=7 Hz), 2.30                               (s,3H), 2.50(s,3H), 3.80(s,3H), 4.80                                          (q,1H,J=7 Hz), 6.80(s,1H), 7.10(t,1H,J=                                       58 Hz), 7.40(s,1H).                                                 5   Oil   C.sub.15 H.sub.15 Cl.sub.2 F.sub.2 N.sub.3 O.sub.4                            NMRδ(CDCl.sub.3): 1.20(t,3H,J=7 Hz), 1.70                               (d,3H,J=7 Hz), 2.50(s,3H), 4.20(q,2H,J=                                       7 Hz), 4.70(q.1H,J=7 Hz), 6.95(s,1H),                                         7.05(t,1H,J=58 Hz), 7.60(s,1H),                                     6   Oil   C.sub.15 H.sub.15 ClF.sub.3 N.sub.3 O.sub.4                                   NMRδ(CDCl.sub.3): 1.20(t,3H,J=7 Hz), 1.70                               (d,3H,J=7 Hz), 2.50(s,3H), 4.20(q,2H,J=                                       7 Hz, 4.70(q,1H,J=7 Hz), 7.00(t,H,J=                                          58 Hz), 7.00-7.40(m,2H).                                            7   Oil   C.sub.16 H.sub.18 ClF.sub.2 N.sub.3 O.sub.4                                   NMRδ(CDCl.sub.3): 1.20(t,3H,J=7 Hz), 1.60                               (d,3H,J=7 Hz), 2.30(s,3H), 2.50(s,3H),                                        4.25(q,2H,J=7 Hz), 4.70(q,1H,J=7 Hz),                                         6.80(s,1H), 7.05(t,1H,J=58 Hz), 7.30                                          (s,1H).                                                             8   Oil   C.sub.15 H.sub.15 Br.sub.2 F.sub.2 N.sub.3 O.sub.4                            NMRδ(CDCl.sub.3): 1.20(t,3H,J=7 Hz), 1.70                               (d,3H,J=7 Hz), 2.45(s,3H), 4.15(q,2H,J=                                       7 Hz), 4.80(q,1H,J=7 Hz), 6.95(s,1H),                                         7.10(t,1H,J=58 Hz), 7.95(s,1H).                                     9   83-88 C.sub.16 H.sub.17 Cl.sub.2 F.sub.2 N.sub.3 O.sub.4                            NMRδ(CDCl.sub.3): 0.90(t,3H,J=7 Hz), 1.20-                              1.90(m,5H), 2.50(s,3H), 4.20(t,2H,J=                                          7 Hz), 4.80(q,1H,J=7 Hz), 7.00(s,1H),                                         7.10(t,1H,J=58 Hz), 7.60(s,1H).                                     10  Oil   C.sub.16 H.sub.17 Cl.sub.2 F.sub.2 N.sub.3 O.sub.4                            NMRδ(CDCl.sub. 3): 1.20(m,6H), 1.70(d,3H,                               J=7 Hz), 2.50(s,3H), 4.60-5.30(m,2H),                                         6.90(s,1H), 7.10(t,1H,J=58 Hz), 7.60                                          (s,1H).                                                             11  Oil   C.sub.17 H.sub.19 Cl.sub.2 F.sub.2 N.sub.3 O.sub.4                            NMRδ (CDCl.sub.3): 0.70-1.70(m,7H), 1.60                                (d,3H,J=7 Hz), 2.45 (s,3H), 4.15(t,2H,                                        J=7 Hz), 4.70(q,1H,J=7 Hz), 6.95(s,1H),                                       7.05(t,1H,J=58 Hz), 7.60(s,1H).                                     12  Oil   C.sub.17 H.sub.19 Cl.sub.2 F.sub.2 N.sub.3 O.sub.4                            NMRδ(CDCl.sub.3): 0.70-1.80(m,11H), 2.50                                (s,3H), 4.40-5.30(m,2H), 7.00(s,1H),                                          7.10(t,1H,J=58 Hz), 7.60(s,1H).                                     13  Oil   C.sub.15 H.sub.16 Cl.sub.2 FN.sub.3 O.sub.4                                                            C 45.94                                                                            4.11                                                                              10.71                                                                F 46.62                                                                            4.16                                                                              12.10                                       NMRδ(CDCl.sub.3): 1.20(t,3H,J=7 Hz), 1.60                               (d,3H,J=7 Hz), 2.35(s,3H), 4.20(q,2H,J=                                       7 Hz), 4.75(q,1H,J=7 Hz), 5.75(d,2H,J=53 Hz),                                 7.00(s,1H), 7.60(s,1H).                                             14  110-111                                                                             C.sub.13 H.sub.11 ClF.sub.3 N.sub.3 O.sub.4                         15  Oil   C.sub.16 H.sub.17 ClF.sub.2 N.sub.3 O.sub.4                         16  Oil   C.sub.16 H.sub.17 ClF.sub.3 N.sub.3 O.sub.4                         17  118-119                                                                             C.sub.14 H.sub.13 Cl.sub.2 F.sub.2 N.sub.3 O.sub.4                                                     C 42.44                                                                            3.31                                                                              10.61                                                                F 42.60                                                                            3.58                                                                              10.53                             18  Oil   C.sub.16 H.sub.17 Cl.sub.2 F.sub.2 N.sub.3 O.sub.4                                                     C 45.30                                                                            4.04                                                                              9.90                                                                 F 44.95                                                                            3.79                                                                              9.70                              19  Oil   C.sub.17 H.sub.19 ClF.sub.3 N.sub.3 O.sub.4                         20  Oil   C.sub.16 H.sub.17 ClF.sub.3 N.sub.3 O.sub.4                                                            C 47.13                                                                            4.20                                                                              10.30                                                                F 47.39                                                                            4.38                                                                              10.35                             21  Oil   C.sub.16 H.sub.17 Cl.sub.2 F.sub.2 N.sub.3 O.sub.4                  22  137-138                                                                             C.sub.16 H.sub.17 ClF.sub.3 N.sub.3 O.sub.4                                                            C 47.13                                                                            4.20                                                                              10.30                                                                F 47.23                                                                            3.94                                                                              9.96                              52  Oil   C.sub.17 H.sub.19 ClF.sub.3 N.sub.3 O.sub.4                         A1  55-56 C.sub.13 H.sub.11 Cl.sub.2 F.sub.2 N.sub.3 O.sub.4                            NMRδ(CDCl.sub.3): 1.70(d,3H,J=7 Hz), 2.50(s,3H),                        4.80(q,1H,J=7 Hz), 7.00(s,1H), 7.10(t,H,J=                                    58 Hz), 7.48(s,1H), 7.50(s,1H).                                     A2  50-55 C.sub.13 H.sub.11 ClF.sub.3 N.sub.3 O.sub.4                                   NMRδ(CDCl.sub.3): 1.70(m,3H), 4.80(m,1H), 2.40                          (s,3H), 7.10-7.50(m,3H), 8.00(bs,1H)                                A3  56-60 C.sub.14 H.sub.14 ClF.sub.2 N.sub.3 O.sub.4                                   NMRδ(CDCl.sub.3 ): 1.60(d,3H,J=7 Hz), 2.30(s,3H),                       2.50(s,3H), 4.70(q,1H,J=7 Hz), 6.80(2,1H),                                    7.00(t,1H,J=58 Hz), 7.30(s,1H), 8.30(s,1H).                         A4  Solid C.sub.13 H.sub.10 ClF.sub.3 N.sub.3 NaO.sub.4                       A5  130-132                                                                             C.sub.12 H.sub.9 ClF.sub.3 N.sub.3 O.sub.4 H.sub.2 O                                                   C 38.99                                                                            3.00                                                                              11.37                                                                F 38.95                                                                            2.91                                                                              11.23                             A6  70-75 C.sub.16 H.sub.20 ClF.sub.3 N.sub.4 O.sub.4                         B1  Oil   C.sub.16 H.sub.16 Cl.sub.2 F.sub.2 N.sub.4 O.sub.6                            NMRδ(CDCl.sub.3): 1.40-1.80(m,6H), 2.50(s,3H),                          4.40-5.00(m,4H), 7.00(s,1H), 7.10(t,1H,J=                                     58 Hz), 7.60(s,1H).                                                 B2  Oil   C.sub.16 H.sub.15 Cl.sub.2 F.sub.2 N.sub.3 O.sub.4                                                     C 45.52                                                                            3.58                                                                              9.95                                                                 F 45.24                                                                            3.46                                                                              9.87                                        NMRδ(CDCl.sub.3): 1.70(d,3H,J=7 Hz), 2.50(s,3H),                        4.60-5.00(m,3H), 5.10-5.40(m,2H), 5.50-6.20                                   (m,1H), 7.00(s,1H), 7.10(t,1H,J=58 Hz), 7.60                                  (s,1H).                                                             B3  Oil   C.sub.16 H.sub.13 Cl.sub.2 F.sub.2 N.sub.3 O.sub.4                            NMRδ(CDCl.sub.3): 1.70(d,3H,J=7 Hz), 2.50(bs,4H),                       4.60-4.90(m,3H), 6.95(s,1H), 7.05(t,1H,J=58 Hz),                              7.60(s,1H).                                                         B4  Oil   C.sub.16 H.sub.13 ClF.sub.3 N.sub.3 O.sub.4                                                            C 47.60                                                                            3.24                                                                              10.41                                                                F 47.88                                                                            3.31                                                                              9.68                                        NMRδ(CDCl.sub.3): 1.65(d,3H,J=7 Hz), 2.45(m,4H),                        4.70(m,3H), 7.05(t,1H,J=58 Hz), 7.10-7.40(m,2H)                     B5  Solid C.sub.16 H.sub.17 Cl.sub.2 F.sub.2 N.sub.3 O.sub.5                  B6  Oil   C.sub.17 H.sub.15 ClF.sub.3 N.sub.3 O.sub.4                                                            C 48.87                                                                            3.62                                                                              10.06                                                                F 46.60                                                                            3.19                                                                              10.01                             B7  Oil   C.sub.18 H.sub.17 ClF.sub.3 N.sub.3 O.sub.4                                                            C 50.07                                                                            3.97                                                                              9.73                                                                 F 49.68                                                                            3.75                                                                              9.40                              B8  Oil   C.sub.18 H.sub.19 ClF.sub.3 N.sub.3 O.sub.5                                                            C 48.06                                                                            4.26                                                                              9.34                                                                 F 48.31                                                                            3.77                                                                              9.00                              B9  Oil   C.sub.16 H.sub.15 ClF.sub.3 N.sub.3 O.sub.6                         B10 Oil   C.sub.18 H.sub.17 ClF.sub.7 N.sub.3 O.sub.4                         B11 Oil   C.sub.15 H.sub.12 ClF.sub.3 N.sub.4 O.sub.4                         B12 Oil   C.sub.18 H.sub.15 ClF.sub.3 N.sub.3 O.sub.5                         B13 Oil   C.sub.17 H.sub.20 ClF.sub.3 N.sub.4 O.sub.4                         B14 Oil   C.sub.17 H.sub.17 ClF.sub.3 N.sub.3 O.sub.5                         B15 Oil   C.sub.19 H.sub.15 ClF.sub.3 N.sub.3 O.sub.4                                                            C 51.66                                                                            3.42                                                                              9.51                                                                 F 52.15                                                                            3.43                                                                              9.49                              B16 Solid C.sub.17 H.sub.15 ClF.sub.3 N.sub.3 O.sub.6                                                            C 45.40                                                                            3.36                                                                              9.34                                                                 F 45.00                                                                            3.25                                                                              8.90                              B17 Oil   C.sub.15 H.sub.15 ClF.sub.3 N.sub.3 O.sub.3 S                       B18 Oil   C.sub.17 H.sub.17 ClF.sub.3 N.sub.3 O.sub.5 S                                                          C 43.64                                                                            3.66                                                                              8.98                                                                 F 43.50                                                                            3.73                                                                              7.99                              B19 Oil   C.sub.14 H.sub.12 Cl.sub.2 F.sub.3 N.sub.3 O.sub.4                            NMRδ(CDCl.sub.3): 1.40(t,3H,J=7 Hz), 2.50(s,3H),                        4.45(q,2H,J=7 Hz), 5.95(d,1H,J=58 Hz), 7.40(s,1H),                            7.50(t,1H,J=58 Hz), 7.65(s,1H).                                     B21 131-136                                                                             C.sub.19 H.sub.22 ClF.sub.3 N.sub.4 O.sub.5                         B22 Oil   C.sub.15 H.sub.15 ClF.sub.3 N.sub.3 O.sub.5                         B23 Oil   C.sub.15 H.sub.15 ClF.sub.3 N.sub.3 O.sub.4 S                       B25 Solid C.sub.15 H.sub.15 ClF.sub.3 N.sub.3 O.sub.6 S                                                          C 39.36                                                                            3.30                                                                              9.18                                                                 F 39.25                                                                            3.00                                                                              9.22                              B30 Oil   C.sub.15 H.sub.12 ClF.sub.6 N.sub.3 O.sub.4                         B31 Oil   C.sub.17 H.sub.16 ClF.sub.3 N.sub.4 O.sub.4                         B32 Oil   C.sub.20 H.sub.17 ClF.sub.3 N.sub.3 O.sub.4                         B33 Oil   C.sub.16 H.sub.17 ClF.sub.3 N.sub.3 O.sub.3 S                       B50 Oil   C.sub.20 H.sub.17 ClF.sub.3 N.sub.3 O.sub.4 S                       B57 Oil   C.sub.17 H.sub.17 ClF.sub.3 N.sub.3 O.sub.6                                                            C 45.19                                                                            3.79                                                                              9.30                                                                 F 45.68                                                                            3.77                                                                              8.22                              C1  209-210                                                                             C.sub.12 H.sub.10 Cl.sub.2 F.sub.2 N.sub.4 O.sub.3                            NMRδ(CDCl.sub.3 /DMSO d.sub.6): 2.20(s,3H), 4.60(s,2H),                 7.30(bs,3H), 7.40(5,1H,J=58 Hz), 7.65(s,1H).                        C2  Oil   C.sub.14 H.sub.14 ClF.sub.3 N.sub.4 O.sub.3                                   NMRδ(CDCl.sub.3): 1.60(d,3H,J=7 Hz), 2.50(s,3H),                        2.90(d,3H,J=7 Hz), 4.75(q,1H,J=7 Hz), 6.80(bs,1H),                            7.10(t,1H,J=58 Hz), 7.20-7.45(m,2H).                                C3  185-188                                                                             C.sub.14 H.sub.14 Cl.sub.2 F.sub.2 N.sub.4 O.sub.5 S                                                   C 36.61                                                                            3.07                                                                              12.20                                                                F 36.79                                                                            3.01                                                                              12.41                                       NMRδ(CDCl.sub.3): 1.70(d,3H,J=7 Hz), 2.50(s,3H),                        3.40(s,3H), 4.80(q,1H,J=7 Hz), 7.10(s,1H),                                    7.10(t,1H,J=58 Hz), 7.70(s,1H).                                     C4  Oil   C.sub.14 H.sub.11 Cl.sub.2 F.sub.5 N.sub.4 O.sub.5 S                                                   C 32.76                                                                            2.16                                                                              10.92                                                                F 32.80                                                                            2.05                                                                              8.77                                        NMRδ(CDCl.sub.3): 1.70(d,3H,J=7 Hz), 2.50(s,3H),                        4.90(q,1H,J=7 Hz), 7.10(s,1H), 7.10(t,1H,J= 58 Hz),                           7.60(s,1H), 8.50(bs,1H).                                            C5  132-135                                                                             C.sub.13 H.sub.12 Cl.sub.2 F.sub.2 N.sub.4 O.sub.3                  C6  142-144                                                                             C.sub.14 H.sub.14 Cl.sub.2 F.sub.2 N.sub.4 O.sub.3                  C7  173-175                                                                             C.sub.12 H.sub.10 ClF.sub.3 N.sub.4 O.sub.3                         C8  105-110                                                                             C.sub.16 H.sub.18 ClF.sub.3 N.sub.4 O.sub.3                         C9  Oil   C.sub.17 H.sub.20 ClF.sub.3 N.sub.4 O.sub.3                         C10 Solid C.sub.20 H.sub.18 ClF.sub.3 N.sub.4 O.sub.5 S                                                          C 46.29                                                                            3.50                                                                              10.80                                                                F 46.77                                                                            4.12                                                                              11.03                             C11 Oil   C.sub.15 H.sub.16 ClF.sub.3 N.sub.4 O.sub.4                                                            C 44.07                                                                            3.94                                                                              13.71                                                                F 38.44                                                                            3.67                                                                              11.28                             C12 Solid C.sub.16 H.sub.14 ClF.sub.3 N.sub.4 O.sub.3                                                            C 47.71                                                                            3.50                                                                              13.91                                                                F 46.03                                                                            3.60                                                                              13.91                             C13 57    C.sub.19 H.sub.16 ClF.sub.3 N.sub.4 O.sub.3                                                            C 51.77                                                                            3.66                                                                              12.71                                                                F 50.90                                                                            4.00                                                                              11.88                             C14 Oil   C.sub.15 H.sub.16 ClF.sub.3 N.sub.4 O.sub.3                         C15 Solid C.sub.17 H.sub.20 ClF.sub.3 N.sub.4 O.sub.3                         C16 Oil   C.sub.15 H.sub.16 ClF.sub.3 N.sub.4 O.sub.3                         C17 Solid C.sub.16 H.sub.16 ClF.sub.3 N.sub.4 O.sub.5                         C18 145-150                                                                             C.sub.14 H.sub.14 ClF.sub.3 N.sub.4 O.sub.5 S                       C19 Solid C.sub.14 H.sub.14 ClF.sub.3 N.sub.4 NaO.sub.5 S                     C20 Solid C.sub.20 H.sub.17 ClF.sub.3 N.sub.4 NaO.sub.5 S                     C21 Oil   C.sub.18 H.sub.18 ClF.sub.3 N.sub.4 O.sub.3                                                            C 50.18                                                                            4.21                                                                              13.00                                                                F 50.95                                                                            3.91                                                                              12.38                             C22 Oil   C.sub.17 H.sub.17 ClF.sub.3 N.sub.5 O.sub.3                         C23 Oil   C.sub.20 H.sub.18 ClF.sub.3 N.sub.4 O.sub.3                         C25 Solid C.sub.19 H.sub.15 Cl.sub.2 F.sub.3 N.sub.4 O.sub.5 S                                                   C 42.31                                                                            2.80                                                                              10.39                                                                F 40.44                                                                            2.91                                                                              8.56                              C26 142-143                                                                             C.sub.13 H.sub.12 ClF.sub.3 N.sub.4 O.sub.3                         C32 127-134                                                                             C.sub.19 H.sub.16 ClF.sub.3 N.sub.4 O.sub.5 S                       C38 47-54 C.sub.17 H.sub.18 ClF.sub.3 N.sub.4 O.sub.3                                                            C 48.75                                                                            4.33                                                                              13.38                                                                F 47.06                                                                            3.73                                                                              12.36                             C42 Oil   C.sub.21 H.sub.18 ClF.sub.3 N.sub.4 O.sub.5 S                       C43 162-166                                                                             C.sub.19 H.sub.15 Cl.sub.2 F.sub.3 N.sub.4 O.sub.5 S                C59 100-105                                                                             C.sub.21 H.sub.18 ClF.sub.3 N.sub.4 O.sub.7 S                                                          C 44.81                                                                            3.40                                                                              9.95                                                                 F 42.20                                                                            2.81                                                                              9.61                              C69 Solid C.sub.19 H.sub.16 ClF.sub.3 N.sub.4 O.sub.5 S                                                          C 45.20                                                                            3.19                                                                              11.10                                                                F 44.74                                                                            3.55                                                                              10.59                             C70 208-108.5                                                                           C.sub.18 H.sub.13 Cl.sub.2 F.sub.3 N.sub.4 O.sub.5 S                                                   C 41.16                                                                            2.49                                                                              10.67                                                                F 44.11                                                                            3.08                                                                              10.96                             C71 Solid C.sub.19 H.sub.14 Cl.sub.2 F.sub.3 N.sub.4 O.sub.5 SNa              C72 135-140                                                                             C.sub.20 H.sub.18 ClF.sub.3 N.sub.4 O.sub.5 S                       C73 Solid C.sub.19 H.sub.15 Cl.sub.2 F.sub.3 N.sub.4 O.sub.5 S                C74 110   C.sub.19 H.sub.15 ClF.sub.3 N.sub.5 O.sub.7 S                       C75 175-180                                                                             C.sub.19 H.sub.14 Cl.sub.3 F.sub.3 N.sub.4 O.sub.5 S                C76 171-173                                                                             C.sub.19 H.sub.15 Cl.sub.3 F.sub.2 N.sub.4 O.sub.5 S                C77 66-70 C.sub.19 H.sub.15 ClF.sub.4 N.sub.4 O.sub.5 S                       C78 248-253                                                                             C.sub.22 H.sub.22 ClF.sub.3 N.sub.4 O.sub.5 S                       C79 Solid C.sub.21 H.sub.20 ClF.sub.3 N.sub.4 O.sub.5 S                       C80 67-70 C.sub.20 H.sub.15 ClF.sub.6 N.sub.4 O.sub.5 S                       C81 58-62 C.sub.20 H.sub.18 ClF.sub.3 N.sub.4 O.sub.6 S                       C82 Solid C.sub.20 H.sub.18 ClF.sub.3 N.sub.4 O.sub.5 S                       C83 108-113                                                                             C.sub.20 H.sub.17 ClF.sub.3 N.sub.4 O.sub.6 SNa                     C84 155-157                                                                             C.sub.20 H.sub.17 Cl.sub.2 F.sub.3 N.sub.4 O.sub.5 S                                                   C 43.41                                                                            3.10                                                                              10.13                                                                F 42.65                                                                            3.30                                                                              9.19                              C85 69-74 C.sub.17 H.sub.14 ClF.sub.3 N.sub.4 O.sub.5 S.sub.2                 C86 Solid C.sub.19 H.sub.20 ClF.sub.3 N.sub.4 O.sub.5                         C87 Solid C.sub.23 H.sub.24 ClF.sub.3 N.sub.4 O.sub.5 S                                                          C 49.24                                                                            4.31                                                                              9.99                                                                 F 46.40                                                                            4.21                                                                              8.63                              C88 Solid C.sub.19 H.sub.17 Cl.sub.2 FN.sub.4 O.sub.5 S                       C89 Solid C.sub.18 H.sub.18 ClF.sub.3 N.sub.4 O.sub.5                         C90 168-172                                                                             C.sub.21 H.sub.20 ClF.sub.3 N.sub.4 O.sub.7 S                       C91 Solid C.sub.21 H.sub.19 ClF.sub.3 N.sub.4 O.sub.7 SNa                     C92 Solid C.sub.20 H.sub.17 ClF.sub.3 N.sub.4 O.sub.5 SNa                     C93 173-179                                                                             C.sub.21 H.sub.18 ClF.sub.3 N.sub.4 O.sub.7 S                       C94 65-70 C.sub.19 H.sub.15 Cl.sub.2 F.sub.3 N.sub.4 O.sub.5 S                C95 110   C.sub.19 H.sub.15 BrClF.sub.3 N.sub.4 O.sub.5 S                                                        C 39.09                                                                            2.59                                                                              9.60                                                                 F 38.75                                                                            2.66                                                                              9.64                              C97 Solid C.sub.20 H.sub.22 ClF.sub.3 N.sub.4 O.sub.5                         C98 Solid C.sub.21 H.sub.17 ClF.sub.3 N.sub.4 O.sub.7 SNa                     C99 Solid C.sub.20 H.sub.17 BrClF.sub.3 N.sub.4 O.sub.6 S                     C100                                                                              Solid C.sub.20 H.sub.16 BrClF.sub.3 N.sub.4 O.sub.6 SNa                   C101                                                                              Solid C.sub.20 H.sub.15 ClF.sub.3 N.sub.5 O.sub.5 S                                                          C 45.33                                                                            2.85                                                                              13.22                                                                F 44.83                                                                            2.42                                                                              13.06                             C102                                                                              60-70 C.sub.18 H.sub.18 ClF.sub.3 N.sub.4 O.sub.5 S                                                          C 43.69                                                                            3.67                                                                              11.32                                                                F 43.24                                                                            4.01                                                                              10.71                             C103                                                                              80-95 C.sub.18 H.sub.18 ClF.sub.3 N.sub.4 O.sub.7 S                       C104                                                                              Oil   C.sub.21 H.sub.24 ClF.sub.3 N.sub.4 O.sub.5                         C105                                                                              Solid C.sub.21 H.sub.20 ClF.sub.3 N.sub. 4 O.sub.7 S                      C106                                                                              Solid C.sub.21 H.sub.19 ClF.sub.3 N.sub.4 O.sub.7 SNa                     C107                                                                              170   C.sub.19 H.sub.15 ClF.sub.3 N.sub.5 O.sub.7 S                       C108                                                                              Solid C.sub.18 H.sub.19 ClF.sub.3 N.sub.5 O.sub.4                         C109                                                                              Oil   C.sub.22 H.sub.22 ClF.sub.3 N.sub.4 O.sub.6 S                       C110                                                                              85-90 C.sub.22 H.sub.21 ClF.sub.3 N.sub.4 O.sub.6 SNa                     C111                                                                              Oil   C.sub.19 H.sub.16 ClF.sub.3 N.sub.4 O.sub.6 S                       C112                                                                              174-176                                                                             C.sub.20 H.sub.18 ClF.sub.3 N.sub.4 O.sub.7 S                       C113                                                                              Oil   C.sub.20 H.sub.17 Cl.sub.2 F.sub.3 N.sub.4 O.sub.5 S                C114                                                                              60-70 C.sub.20 H.sub.16 Cl.sub.2 F.sub.3 N.sub.4 O.sub.5 SNa              C115                                                                              Solid C.sub.19 H.sub.15 BrClF.sub.3 N.sub.4 O.sub.5 S                     C116                                                                              188-191                                                                             C.sub.20 H.sub.16 ClF.sub.3 N.sub.4 O.sub.7 S                       C117                                                                              >230  C.sub.23 H.sub.18 ClF.sub.3 N.sub.4 O.sub.5 S                       C118                                                                              144-147                                                                             C.sub.21 H.sub.19 Cl.sub.3 F.sub.2 N.sub.4 O.sub.7 S                C119                                                                              211-212                                                                             C.sub.20 H.sub.18 ClF.sub.3 N.sub.4 O.sub.7 S                       C120                                                                              Solid C.sub.20 H.sub.17 ClF.sub.3 N.sub.4 O.sub.7 SNa                     C121                                                                              Solid C.sub.20 H.sub.17 ClF.sub.3 N.sub.4 O.sub.7 SNa                     C122                                                                              105-110                                                                             C.sub.21 H.sub.20 Cl.sub.2 F.sub.2 N.sub.4 O.sub.7 S                C123                                                                              163-166                                                                             C.sub.21 H.sub.20 BrF.sub.3 N.sub.4 SO.sub.7                        C124                                                                              Solid C.sub.21 H.sub.21 ClF.sub.3 N.sub.5 O.sub.5 S                       C125                                                                              Solid C.sub.20 H.sub.15 ClF.sub.6 N.sub.4 O.sub.6 S                       C126                                                                              Solid C.sub.20 H.sub.17 ClF.sub.3 N.sub.5 O.sub.7 S                       C127                                                                              Solid C.sub.28 H.sub.34 ClF.sub.3 N.sub.4 F.sub.3 O.sub.5 S               C128                                                                              Solid C.sub.28 H.sub.33 ClF.sub.3 N.sub.4 O.sub.5 SNa                     C129                                                                              147-149                                                                             C.sub.19 H.sub.16 ClF.sub.3 N.sub.4 O.sub.6 S                                                          C 43.81                                                                            3.10                                                                              10.76                                                                F 44.31                                                                            3.26                                                                              10.54                             C130                                                                              Solid C.sub.19 H.sub.15 ClF.sub.3 N.sub.4 O.sub.6 SNa                     C131                                                                              198-201                                                                             C.sub.23 H.sub.22 ClF.sub.3 N.sub.4 O.sub.6 S                                                          C 48.05                                                                            3.86                                                                              9.74                                                                 F 47.11                                                                            3.89                                                                              9.34                              C132                                                                              Solid C.sub.20 H.sub.14 ClF.sub.6 N.sub.4 O.sub.6 SNa                     C133                                                                              Solid C.sub.20 H.sub.15 BrF.sub.6 N.sub.4 O.sub.6 S                       C134                                                                              65-68 C.sub.20 H.sub.17 ClF.sub.4 N.sub.4 O.sub.6 S                       C135                                                                              68-72 C.sub.20 H.sub.17 ClF.sub.4 N.sub.4 O.sub.6 S                       C136                                                                              Solid C.sub.21 H.sub.20 ClF.sub.3 N.sub.4 O.sub.6 S                       C137                                                                              130-134                                                                             C.sub.20 H.sub.17 ClF.sub.4 N.sub.4 O.sub.3                         C138                                                                              136-140                                                                             C.sub.23 H.sub.18 ClF.sub.3 N.sub.4 O.sub.5 S                       C139                                                                              Solid C.sub.21 H.sub.19 ClF.sub.3 N.sub.4 O.sub.6 SNa                     __________________________________________________________________________

    TABLE 7      Preemergence Herbicidal Activity       Compound No. 1 2 3 4 6 7 8 9 10 11 12 13 14 Rate (kg/ha) 2.0 4.0 2.0     2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 1.0 Species % K % C % K % C % K % C     % K % C % K % C % K % C % K % C % K % C % K % C % K % C % K % C % K % C     % K % C       Cotton  100 100   100 50   100  60  70  100  100  40  100  30  90     Soybean  0 90   30 0   10  30  20  20  20  100  30  20  0 Field Corn  80     100   100 30   70  30  20  80  100  40  20  20  60 Rice  50 100   90 30      80  50  60  90  90  90  70  10  30 Wheat  0 100   100 30   100  80  40     90  90  70  50  10  20 Field Bindweed  100 100   100 100   100  60  80     100  100  100  90  20  100 Morningglory  100 100   60 0   100  70  90     100  100  100  100  50  90 Velvetleaf  100 100   ND 100   100  100  100     100  100  100  100  80  100 Barnyardgrass  90 100   100 100   100  100     100  100  100  100  100  40  50 Green Foxtail  100 100   100 ND   100     100  100  100  100  100  100  40  10 Johnsongrass  80 100   100 95   90     90  90  100  100  100  90  40  60 Yellow Nutsedge  70 100   100 0   100     50  80  100  100  90  90  10  100       Compound No. 15 16 17 18 19 20 21 51 52 A1 A2 A3 A4 Rate (kg/ha) 1.0     1.0 2.0 0.5 2.0 0.5 2.0 2.0 2.0 4.0 2.0 2.0 1.0 Species % K % C % K % C     % K % C % K % C % K % C % K % C % K % C % K % C % K % C % K % C % K % C     % K % C % K % C       Cotton  100  100  100  10  80  30  80  70  100 100   10 80   90     Soybean  40  30  0  20  100  0  20  10  70 0   0 20   10 Field Corn  40     100  30  10  80  0  80  30  100 0   0 0   40 Rice  80  90  30  0  90  20      30  40  95 80   10 70   80 Wheat  100  100  10  0  50  0  0  0  100 80      20 100   80 Field Bindweed  90  100  90  0  100  90  100  90  100 100     30 50   70 Morningglory  100  90  90  0  90  90  90  80  95 100   10 0     90 Velvetleaf  100  100  90  30  100  100  100  100  100 100   ND 100     100 Barnyardgrass  100  100  90  0  100  50  100  30  100 100   40 100     100 Green Foxtail  100  100  10  90  100  100  100  20  100 100   100 ND       100 Johnsongrass  90  90  80  0  90  30  90  80  100 80   30 95   90     Yellow Nutsedge  90  100  60  0  100  10  70  40  100 90   20 0     90       Compound No. A6 B1 B2 B3 B4 B5 B6 B7 B8 B9 B10 B11 B12 Rate     (kg/ha) 0.5 2.0 2.0 2.0 1.0 2.0 1.0 1.0 2.0 0.5 1.0 1.0 1.0  Species % K %      C % K % C % K % C % K % C % K % C % K % C % K % C % K % C % K % C % K %     C % K % C % K % C % K % C       Cotton  80  100  100  100  90  100  100  100  100  100  20  100  100     Soybean  30  10  10  0  40  20  10  30  50  20  0  10  10 Field Corn  30      30  90  30  80  50  40  80  100  30  30  60  20 Rice  30  90  90  70     80  90  90  90  90  60  30  60  60 Wheat  30  70  90  80  90  90  90  80      90  40  70  90  50 Field Bindweed  70  100  100  90  100  100  90  100     100  80  100  100  70 Morningglory  90  100  100  100  90  90  100  100     100  60  90  90  90 Velvetleaf  90  100  100  100  100  100  100  100     100  100  100  100  100 Barnyardgrass  100  100  100  100  100  100  100      100  100  100  100  100  100 Green Foxtail  100  100  100  100  100     100  100  100  100  100  100  100  100 Johnsongrass  80  90  100  100     90  100  90  80  100  50  80  90  80 Yellow Nutsedge  80  100  100  100     90  100  100  100  100  100  70  100  90       Compound No. B13 B14 B15 B16 B17 B18 B21 B22 B23 B25 B30 B31 B32 Rate     (kg/ha) 1.0 1.0 2.0 1.0 1.0 2.0 1.0 0.5 1.0 1.0 0.5 1.0 0.5 Species % K     % C % K % C % K % C % K % C % K % C % K % C % K % C % K % C % K % C % K     % C % K % C % K % C % K % C       Cotton  90  100  100  80  100  100  90  60  70  70  100  100  20     Soybean  100  20  70  20  40  30  0  0  0  50  0  10  0 Field Corn  90     40  90  60  80  60  50  0  30  70  10  20  20 Rice  90  80  90  60  80     80  40  40  80  60  20  50  20 Wheat  90  90  90  50  90  90  50  10  60      50  20  30  10 Field Bindweed  100  90  100  90  80  100  90  20  90     70  20  70  30 Morningglory  100  100  100  100  100  100  90  40  100     100  50  80  30 Velvetleaf  100  100  100  100  100  100  100  100  100     100  100  100  90 Barnyardgrass  100  100  100  100  100  100  100  80     90  100  100  100  100 Green Foxtail  100  100  100  100  90  100  90     80  100  100  100  100  100 Johnsongrass  90  90  100  90  90  90  40     20  70  90  50  80  50 Yellow Nutsedge  90  90  100  100  100  100  90     90  80  90  100  90  90       Compound No. B33 B50 B57 C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 Rate (kg/ha)     1.0 0.5 0.5 2.0 1.0 2.0 2.0 2.0 2.0 1.0 2.0 1.0 1.0 Species % K % C % K     % C % K % C % K % C % K % C % K % C % K % C % K % C % K % C % K % C % K     % C % K % C % K % C       Cotton  80  50  100  70  100  100  40  100  100  100  90  80  100     Soybean  40  20  10  40  100  40  0  100  90  10  100  90  90 Field Corn      90  30  40  60  100  80  0  100  100  100  100  100  20 Rice  90  40     50  20  100  80  0  100  100  40  100  90  80 Wheat  60  60  60  20  100      90  40  100  100  30  100  100  70 Field Bindweed  90  10  90  100  100      100  80  100  100  100  100  100  100 Morningglory  90  50  70  100     100  100  90  100  90  100  100  100  100 Velvetleaf  100  100  100  100      100  100  100  100  100  100  100  100  100 Barnyardgrass  100  90  100      80  100  100  90  100  100  100  100  100  100 Green Foxtail  100  100     100  90  100  100  90  100  100  90  100  100  100 Johnsongrass  70  50     70  80  100  100  50  100  100  90  100  100  90 Yellow Nutsedge  90  50      90  80  100  100  50  100  100  100  90  80  60       Compound No. C11 C12 C13 C14 C15 C16 C17 C18 C19 C20 C21 C22 C23 Rate     (kg/ha) 1.0 1.0 2.0 2.0 2.0 2.0 2.0 1.0 1.0 1.0 1.0 1.0 1.0 Species % K     % C % K % C % K % C % K % C % K % C % K % C % K % C % K % C % K % C % K     % C % K % C % K % C % K % C       Cotton  100  100  100  100  100  100  100  100  100  100  100  100  30     Soybean  100  100  100  100  100  100  100  0  20  80  90  100  50 Field     Corn  100  100  90  100  100  100  100  70  100  50  100  100  90 Rice     100  100  100  100  100  100  90  80  60  30  80  100  20 Wheat  100     100  90  100  100  100  90  50  40  10  100  100  70 Field Bindweed  100      100  100  100  100  100  100  80  80  100  100  100  100 Morningglory     100  100  100  100  100  100  100  100  100  100  100  100  100 Velvetlea     f  100  100  100  100  100  100  100  100  100  100  100  100  100     Barnyardgrass  100  100  100  100  100  100  100  100  100  100  100     100  100 Green Foxtail  100  100  100  100  100  100  100  100  100  100      100  100  100 Johnsongrass  100  100  100  100  100  100  100  90  90     40  100  100  100 Yellow Nutsedge  100  100  100  100  100  100  100  90      80  10  80  100  40       Compound No. C24 C25 C26 C32 C38 C42 C43 C59 C69 C70 C71 C72 C73 Rate     (kg/ha) 1.0 2.0 1.0 1.0 1.0 1.0 1.0 1.0 0.5 1.0 1.0 1.0 1.0 Species % K     % C % K % C % K % C % K % C % K % C % K % C % K % C % K % C % K % C % K     % C % K % C % K % C % K % C       Cotton  40  100  100  100  90  90  100  100  40  100  100  100  80     Soybean  10  30  100  40  100  70  70  50  10  20  50  50  30 Field Corn      80  70  100  20  100  40  70  70  30  30  50  60  30 Rice  30  60  90     50  100  60  90  80  30  70  40  30  40 Wheat  0  30  100  10  100  70     70  40  0  20  40  20  50 Field Bindweed  90  100  100  100  100  100     100  100  90  100  100  100  100 Morningglory  100  100  100  100  100     100  100  100  80  100  100  100  100 Velvetleaf  90  100  100  100  100      100  100  100  100  100  100  100  100 Barnyardgrass  80  100  100  100      100  100  100  100  20  20  90  100  90 Green Foxtail  100  90  100  80      100  100  100  100  20  0  40  95  100 Johnsongrass  70  70  100  80     100  60  95  100  40  80  60  90  80 Yellow Nutsedge  30  80  100  40     ND  70  100  70  70  90  40  60  20       Compound No. C74 C75 C76 C77 C78 C79 C80 C81 C82 C83 C84 C85 C86 Rate     (kg/ha) 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 2.0 Species % K     % C % K % C % K % C % K % C % K % C % K % C % K % C % K % C % K % C % K     % C % K  % C % K % C % K % C       Cotton  100  90  60  95  80  50  60  100  100  95  10  100  100     Soybean  80  30  30  40  40  0  20  100  10  95  0  30  70 Field Corn  0      50  20  30  30  10  0  50  20  20  10  95  100 Rice  40  60  30  70  50      50  20  50  30  40  20  80  90 Wheat  30  40  20  60  40  20  30  100     20  30  0  80  90 Field Bindweed  90  100  100  100  100  80  100  100     100  100  30  100  100 Morningglory  100  100  100  100  100  100  100     100  100  100  100  100  100 Velvetleaf  100  100  100  100  100  100     100  100  100  100  90  100  100 Barnyardgrass  85  95  100  100  100     80  95  100  95  95  10  100  100 Green Foxtail  100  95  70  100  90     100  100  100  100  90  30  100  100 Johnsongrass  70  80  40  95  40     80  95  100  95  80  30  100  100 Yellow Nutsedge  20  30  30  30  30     20  0  80  10  20  ND  ND  ND       Compound No. C87 C88 C89 C90 C91 C92 C93 C94 C95 C97 C98 C99 C100 Rate     (kg/ha) 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 0.5 0.5  0.5 Species % K %      C % K % C % K % C % K % C % K % C % K % C % K % C % K % C % K % C % K %     C % K % C % K % C % K % C       Cotton  30  0  90  100  100  100  20  80  100  100  100  80  80     Soybean  20  10  30  100  90  30  0  20  60  20  30  70  50 Field Corn     10  10  60  80  80  20  30  20  20  70  40  30  60 Rice  40  0  90  80     90  40  50  20  30  80  20  20  60 Wheat  10  0  80  70  50  30  10  0     10  70  20  10  20 Field Bindweed  100  0  100  100  100  100  80  100     100  100  100  100  100 Morningglory  100  0  100  100  100  100  80     100  100  100  100  100  100 Velvetleaf  100  10  100  100  100  100     100  100  100  100  100  100  100 Barnyardgrass  95  40  100  100  100     100  100  60  40  100  90  10  70 Green Foxtail  0  0  100  100  100     100  0  50  50  100  80  100  80 Johnsongrass  30  10  95  100  95  80     30  60  60  90  95  80  80 Yellow Nutsedge  ND  ND  ND  ND  ND  ND  ND     ND  ND  ND  ND  ND  ND       Compound No. C101 C102 C103 C104 C105 C106 C107 C108 C109 C110 C111     C112 C113 Rate (kg/ha) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5     0.5 Species % K % C % K % C % K % C % K % C % K % C % K % C % K % C % K     % C % K % C % K % C % K % C % K % C % K % C       Cotton  95  30  30  30  100  100  90  100  70  30  20  90  50 Soybean     30  20  10  10  95  90  10  95  90  95  40  40  0 Field Corn  10  50  30      90  70  30  20  100  100  100  10  0  10 Rice  20  80  50  80  95  90     40  95  95  90  70  20  20 Wheat  10  50  30  80  50  30  0  95  100     100  50  10  10 Field Bindweed  90  20  40  100  100  100  80  90  95     100  70  100  100 Morningglory  100  80  60  90  100  100  95  100  100     100  70  90  90 Velvetleaf  100  100  100  100  100  100  100  100  100     100  90  100  100 Barnyardgrass  60  100  95  95  100  100  40  80  100     100  100  40  50 Green Foxtail  40  100  100  100  100  100  0  100  100      100  100  80  30 Johnsongrass  50  80  80  95  100  100  50  100  100     100  70  95  30 Yellow Nutsedge  ND  ND  ND  ND  ND  ND  ND  ND  ND  ND     ND  ND  ND       Compound No. C114 C115 C116 C117 C118 C119 C120 C121 C122 C123 C124     C125 Rate (kg/ha) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.25 0.5 0.5     Species % K % C % K % C % K % C % K % C % K % C % K % C % K % C % K % C     % K % C % K % C % K % C  % K % C       Cotton  30  80  95  50  20  50  70  95  70  50  20  20 Soybean  0  30     0  95  0  30  20  20  50  50  60  30 Field Corn  10  10  10  10  10  10     10  20  40  0  70  10 Rice  20  10  20  30  0  30  20  30  0  60  80  10     Wheat  10  30  10  0  10  30  10  10  10  10  60  10 Field Bindweed  90     100  90  100  80  100  100  100  100  100  100  80 Morningglory  95  100      95  100  50  100  90  90  80  100  95  90 Velvetleaf  100  100  100     100  50  100  100  100  100  100  100  100 Barnyardgrass  70  50  80  40      10  50  80  70  70  100  100  30 Green Foxtail  70  90  40  80  10  0     0  20  50  10  100  50 Johnsongrass  70  90  80  20  10  70  70  90  100      100  100  10 Yellow Nutsedge  ND  ND  ND  ND  ND  ND  ND  ND  ND  ND     ND  ND

    TABLE 8      Postemergence Herbicidal Activity       Compound No. 1 2 3 4 6 7 8 9 10 11 12 13 14 Rate (kg/ha) 2.0 4.0 2.0     2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 1.0 Species % K % C % K % C % K % C     % K % C % K % C % K % C % K % C % K % C % K % C % K % C % K % C % K % C     % K % C       Cotton  100 100   100 90   100  90  100  100  100  100  100  70  100     Soybean  40 0   60 0   50  40  50  30  30  50  30  20  60 Field Corn  90     100   100 0   100  40  30  100  100  60  30  10  10 Rice  80 100   100     80   100  80  90  70  90  90  50  30  30 Wheat  10 100   90 90   100  90      30  80  100  90  70  20  10 Field Bindweed  100 100   100 100   100     100  100  100  100  100  100  50  100 Morningglory  100 100   100 70     100  80  100  80  30  100  100  80  100 Velvetleaf  100 100   ND 100     100  100  100  100  100  100  100  80  100 Barnyardgrass  100 100   100     90   100  100  100  100  90  100  100  80  100 Green Foxtail  100 100     ND ND   100  100  100  100  100  100  100  40  90 Johnsongrass  90 95     100 70   100  100  70  80  80  80  90  30  80 Yellow Nutsedge  50 50     100 0   100  70  30  80  90  90  50  20  30       Compound No. 15  16 17 18 19 20 21 51 52 A1 A2 A3 A4 Rate (kg/ha) 1.0     1.0 2.0 0.5 2.0 0.5 2.0 2.0 2.0 4.0 2.0 2.0 1.0 Species % K % C % K % C     % K % C % K % C % K % C % K % C % K % C % K % C % K  % C % K % C % K % C %      K % C % K % C       Cotton  100  100  100  100  100  90  80  70  100 100   90 100   100     Soybean  40  30  70  30  40  40  20  50  95 0   20 0   40 Field Corn  30      10  70  60  50  30  20  10  100 0   30 0   40 Rice  90  30  30  20  50     20  30  30  90 30   20 90   20 Wheat  60  40  20  20  30  30  20  10     100 30   30 80   90 Field Bindweed  100  90  90  50  80  40  90  90  100     100   80 100   90 Morningglory  100  100  100  50  90  80  100  100  100     100   70 60   100 Velvetleaf  100  100  100  80  100  100  100  90  100     100   ND 100   100 Barnyardgrass  100  100  70  10  80  80  14  70  100     100   90 100   100 Green Foxtail  100  100  20  60  80  60  30  10  100     100   ND ND   100 Johnsongrass  90  80  70  30  40  10  40  40  100 75     60 95   60 Yellow Nutsedge  80  90  30  10  90  10  30  30  100 0   10 0       100       Compound No. A6 B1 B2 B3 B4 B5 B6 B7 B8 B10 B11 B12 B13 Rate (kg/ha)     0.5 2.0 2.0 2.0 1.0 2.0 1.0 1.0 2.0 1.0 1.0 1.0 1.0 Species % K % C % K     % C % K % C % K % C % K % C % K % C % K % C % K % C % K % C % K % C % K     % C % K % C % K % C       Cotton  90  100  100  100  100  100  100  100  100  100  100  100  100     Soybean  20  10  30  30  40  60  60  60  80  20  30  30  100 Field Corn     20  40  30  70  30  20  100  100  70  0  0  10  60 Rice  30  50  80  90     90  80  100  100  100  20  30  20  50 Wheat  90  100  100  90  100  90     100  100  100  10  100  100  90 Field Bindweed  10  100  100  100  100     100  90  100  100  100  100  100  100 Morningglory  90  100  40  80  90     100  100  100  100  100  100  100  100 Velvetleaf  100  100  100  100     100  100  100  100  100  100  100  100  100 Barnyardgrass  100  100  100      100  100  100  100  100  100  100  100  100  100 Green Foxtail  90  100      100  100  100  100  100  100  100  100  100  100  100 Johnsongrass  30     80  80  90  80  90  80  80  70  90  90  30  100 Yellow Nutsedge  50  40     80  30  90  60  100  80  70  20  100  90  100       Compound No. B14 B15 B16 B17 B18 B21 B22 B23 B25 B30 B31 B32 B33 Rate     (kg/ha) 1.0 2.0 1.0 1.0 2.0 1.0 0.5 1.0 1.0 0.5 1.0 0.5 1.0 Species % K     % C % K % C % K % C % K % C % K % C % K % C % K % C % K % C % K % C % K     % C % K % C % K % C % K % C       Cotton  100  100  100  100  100  100  80  100  80  80  100  100  100     Soybean  90  80  40  40  50  30  30  10  30  10  20  10  30 Field Corn     20  60  30  30  20  30  20  40  90  10  40  0  40 Rice  80  90  50  30     90  20  70  90  50  70  40  20  40 Wheat  80  100  100  40  70  100  90     80  90  100  80  70  100 Field Bindweed  90  100  100  100  100  100  50      100  100  50  100  80  100 Morningglory  90  100  80  90  100  100  100      100  100  100  90  100  100 Velvetleaf  100  100  100  100  100  90     100  100  100  100  90  100  100 Barnyardgrass  100  100  100  70  100     100  100  60  100  100  100  100  100 Green Foxtail  100  100  100  100     100  100  100  100  100  100  100  100  100 Johnsongrass  60  100  40     30  40  10  10  100  50  10  50  0  40 Yellow Nutsedge  70  90  100  60     90  80  10  90  90  10  90  0  60       Compound No. B50 B57 C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 Rate (kg/ha)     0.5 0.5 2.0 1.0 2.0 2.0 2.0 2.0 1.0 2.0 1.0 1.0 1.0 Species % K % C % K     % C % K % C % K % C % K % C % K % C % K % C % K % C % K % C % K % C % K     % C % K % C % K % C       Cotton  100  100  100  100  100  70  100  100  100  100  90  100  100     Soybean  30  30  30  90  40  40  90  90  60  90  80  100  90 Field Corn     20  30  70  100  100  40  100  100  50  90  80  60  100 Rice  40  90  20      100  70  50  100  100  80  80  50  60  100 Wheat  40  90  0  100  40     30  100  100  10  80  60  60  100 Field Bindweed  70  80  100  100  90     100  100  100  100  100  90  60  90 Morningglory  100  100  100  100     100  90  100  100  100  100  80  100  100 Velvetleaf  100  100  100  100      100  100  100  100  100  100  100  100  100 Barnyardgrass  100  100     100  100  100  90  100  100  100  60  100  100  100 Green Foxtail  100     100  100  100  100  90  100  100  100  100  100  100  100 Johnsongrass     30  40  80  100  90  40  90  100  90  80  90  80  90 Yellow Nutsedge  20      60  60  100  30  20  100  100  80  60  20  10  100       Compound No. C12 C13 C14 C15 C16 C17 C18 C19 C20 C21 C22 C23 C24 Rate     (kg/ha) 1.0 2.0 2.0 2.0 2.0  2.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Species % K %      C % K % C % K % C % K % C % K % C % K % C % K % C % K % C % K % C % K %     C % K % C % K % C % K % C       Cotton  100  100  100  100  100  100  100  100  100  100  100  100  50     Soybean  90  80  100  90  100  100  40  40  100  100  100  80  20 Field     Corn  100  100  100  90  100  100  30  20  0  100  100  80  2O Rice  100      100  70  50  90  100  10  10  20  60  80  30  10 Wheat  100  100  100     100  100  100  100  100  100  100  100  90  10 Field Bindweed  100  100     100  100  100  90  100  100  100  100  100  100  100 Morningglory  100     100  100  100  100  100  100  100  100  100  100  80  90 Velvetleaf  100      100  100  100  100  100  100  100  100  100  100  100  100 Barnyardgrass       100  100  100  100  100  100  100  100  100  100  100  100  80 Green     Foxtail  100  100  100  100  100  100  100  100  100  100  100  100  100     Johnsongrass  100  100  100  90  100  50  90  100  40  100  100  100  60     Yellow Nutsedge  100  100  100  90  100  100  100  60  10  80  80  40     0   Compound No. C25 C26 C32 C38 C42 C43 C59 C69 C70 C71 C72 C73 C74     Rate (kg/ha) 2.0 1.0 1.0 1.0 1.0 1.0 1.0 0.5 1.0 1.0 1.0 1.0 1.0 Species %      K % C % K % C % K % C % K % C % K % C % K % C % K % C % K % C % K % C %     K % C % K % C % K % C % K % C       Cotton  100  100  100  100  100  100  100  100  90  100  100  100  85     Soybean  70  80  80  100  100  90  80  50  60  60  70  85  90 Field Corn      60  100  20  100  100  100  80  80  40  60  50  30  40 Rice  50  90  50      100  60  50  40  60  30  40  60  60  60 Wheat  60  90  50  100  90  95     80  90  40  95  30  80  50 Field Bindweed  100  100  100  70  100  100     100  100  100  100  100  100  95 Morningglory  100  100  100  100  95     100  100  100  100  100  100  100  100 Velvetleaf  100  100  100  100     100  100  100  100  100  100  100  100  100 Barnyardgrass  100  100  100      100  95  100  100  100  100  100  100  90  100 Green Foxtail  100  100     80  100  100  100  100  50  30  100  60  90  85 Johnsongrass  100  90     40  90  95  100  95  60  70  50  50  70  50 Yellow Nutsedge  70  90  20     ND  40  95  100  50  40  20  60  30  30       Compound No. C75 C76 C77 C78 C79 C80 C81 C82 C83 C84 C85 C86 C87 Rate     (kg/ha) 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 2.0 1.0 Species % K     % C % K % C % K % C % K % C % K % C % K % C % K % C % K % C % K % C % K     % C % K % C % K % C % K % C       Cotton  95  95  100  100  100  100  100  100  100  80  100  100  90     Soybean  90  80  80  100  50  80  100  80  100  40  90  80  100 Field     Corn  100  70  100  100  20  40  80  100  95  40  95  100  100 Rice  40     40  30  30  20  10  90  70  60  20  95  100  50 Wheat  40  30  100  90     40  40  95  90  90  30  80  100  60 Field Bindweed  100  100  100  100     50  100  100  100  100  20  95  100  100 Morningglory  100  95  100  100      60  100  100  100  100  90  100  100  100 Velvetleaf  100  100  100     100  100  100  100  100  100  100  100  100  100 Barnyardgrass  95  95     95  100  100  40  100  100  100  95  100  100  100 Green Foxtail  100     95  100  90  95  100  100  100  100  30  100  100  80 Johnsongrass  80     40  70  60  80  40  100  100  95  20  90  100  30 Yellow Nutsedge  10     20  30  20  70  20  20  0  60  ND  ND  ND  ND       Compound No. C88 C89 C90 C91 C92 C93 C94 C95 C97 C98 C99 C100 C101     Rate (kg/ha) 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 0.5 0.5 0.5 0.5 Species %      K % C % K % C % K % C % K % C % K % C % K % C % K % C % K % C % K % C %     K % C % K % C % K % C % K % C       Cotton  10  90  100  100  100  100  100  100  95  90  90  100  100     Soybean  30  90  100  100  90  70  80  95  95  70  100  100  60 Field     Corn  20  100  95  100  100  70  50  95  100  70  100  100  50 Rice  10     70  60  90  70  30  30  70  95  70  40  40  20 Wheat  10  100  100  100     80  80  40  100  100  90  100  100  40 Field Bindweed  10  95  100  100     100  70  95  100  95  100  100  100  90 Morningglory  20  100  100  100     100  95  100  100  100  100  100  100  90 Velvetleaf  20  100  100  100     100  100  100  100  100  100  100  100  100 Barnyardgrass  20  100  100     100  100  100  80  90  95  95  100  100  30 Green Foxtail  50  100  100     100  80  95  95  100  100  70  90  100  10 Johnsongrass  30  80  100     100  70  30  60  70  95  90  100  90  50 Yellow Nutsedge  ND  ND  ND  ND      ND  ND  ND  ND  ND  ND  ND  ND  ND       Compound No. C102 C103 C104 C105 C106 C107 C108 C109 C110 C111 C112     C113 C114 Rate (kg/ha) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5     0.5 Species % K % C % K % C % K % C % K % C % K % C % K % C % K % C % K     % C % K % C % K % C % K % C % K % C % K % C       Cotton  100  100  80  100  100  100  100  95  80  40  90  80  95     Soybean  50  30  80  100  100  60  100  95  100  50  90  40  50 Field     Corn  60  30  90  95  100  60  100  80  90  20  40  30  30 Rice  70  40     70  95  95  20  95  80  80  20  20  30  80 Wheat  95  30  90  100  100     20  100  95  95  70  90  30  30 Field Bindweed  90  95  50  100  100     100  100  100  100  60  100  100  100 Morningglory  100  95  90  100     100  100  100  100  100  100  100  100  100 Velvetleaf  95  100  100     100  100  100  100  100  100  100  100  100  100 Barnyardgrass  60  60     95  100  100  95  100  100  100  100  95  30  70 Green Foxtail  100  100      95  100  100  90  100  100  100  100  100  80  90 Johnsongrass  70  70     80  100  100  60  100  100  100  95  95  40  30 Yellow Nutsedge  ND  ND     ND  ND  ND  ND  ND  ND  ND  ND  ND  ND  ND       Compound No. C115 C116 C117 C118 C119 C120 C121 C122 C123 C124 C125     Rate (kg/ha) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.25 0.5 0.5 Species % K %     C % K % C % K % C % K % C % K % C % K % C % K % C % K % C % K % C % K %     C % K % C       Cotton  20  100  100  40  95  80  100  95  100  100  100 Soybean  30     60  100  95  95  95  80  80  100  100  100 Field Corn  30  40  100  100     40  60  10  60  90  100  100 Rice  10  20  0  10  10  10  20  10  90  70      0 Wheat  30  60  95  60  90  100  100  100  100  100  100 Field     Bindweed  10  80  100  95  100  100  100  95  100  100  100 Morningglory      30  100  100  80  100  100  100  100  100  100  100 Velvetleaf  20  100      100  100  100  100  100  100  100  100  100 Barnyardgrass  20  70  100     60  50  50  80  100  95  100  95 Green Foxtail  30  70  100  40  70  20     30  80  95  100  95 Johnsongrass  30  80  70  20  60  40  80  80  95  95      90 Yellow Nutsedge  ND  ND  ND  ND  ND  ND  ND  ND  ND  ND  ND

I claim:
 1. An herbicidal compound of the formula: ##STR200## wherein R⁴is ethyl.
 2. An herbicidal composition comprising an herbicidallyeffective amount of the compound of claim 1 in admixture with a suitablecarrier.
 3. A method for controlling undesired plant growth whichcomprises applying to the locus where control is desired an herbicidallyeffective amount of the composition of claim 2.